Cellulose resin and process for producing the same

ABSTRACT

A cellulose resin produced by binding a hydrogenated cardanol containing 3-pentadecylcyclohexanol, and cellulose or a derivative thereof through the reaction between a hydroxy group of the hydrogenated cardanol, a hydroxy group of the cellulose or a derivative thereof and isocyanate groups of a diisocyanate compound.

TECHNICAL FIELD

The present invention relates to a cellulose resin and a process forproducing the same.

BACKGROUND ART

Bioplastic using a plant as a raw material can contribute to acountermeasure against petroleum depletion and global warming and hasbeen started being used not only in common products such as packaging,containers and fibers but also in durable products such as electronicsand automobiles.

However, general bioplastics, such as polylactic acid,polyhydroxyalkanoate and modified starch, all use starch materials, moreprecisely, edible parts, as raw materials. Accordingly, for fear offuture food shortage, it has been desired to develop a novel bioplasticusing a non-edible part as a raw material.

As bioplastic using a non-edible part as a raw material, various typesof bioplastics using cellulose, which is a main component of non-edibleparts of wood and plant, have been already developed and commercialized.

Cellulose is a high molecular weight compound formed by polymerizationof β-glucose. Since cellulose has high crystallinity, it is hard,fragile and absent of thermoplasticity. In addition, since cellulosecontains many hydroxy groups, water absorbability is high and waterresistance is low. Then, various investigations have been made toimprove the properties of cellulose.

For example, Patent Literature 1 (JP11-255801A) discloses abiodegradable graft polymer having thermoplasticity obtained byring-opening graft polymerization of ε-caprolactone with celluloseacetate having a hydroxy group.

Meanwhile, a material using a component of a non-edible part other thancellulose has been developed. For example, cardanol derived from cashewnutshell, since it has stable amount of production and excellentfunctionality ascribed to its characteristic molecular structure, hasfound various applications.

As an example of using cardanol, Patent Literature 2 (JP10-8035A)discloses a friction material for brake, which is formed of a fiber basematerial made of an aramid pulp and a cellulose fiber, and a filler madeof calcium carbonate and cashew dust, with the use of a binder made of aphenol resin. Patent Literature 3 (JP2001-32869A) discloses a frictionmaterial which is formed of a base material made of an aramid fiber anda cellulose fiber, and a filler made of graphite and cashew dust, withthe use of an organic/inorganic composite binder. It is described thatthe friction material is applied to clutch facing of a powertransmission system of automobiles etc.

In Non Patent Literature 1 (George John et al., Polymer Bulletin, 22, p.89-94 (1989)), it is described that water resistance of paper can beimproved by soaking a paper sheet in cardanol to perform a graftingreaction through which cardanol binds to cellulose constituting thepaper sheet. It is described that, in the grafting reaction, a terminaldouble bond of cardanol binds to a hydroxy group of cellulose in thepresence of boron trifluoride diethyl ether (BF₃—OEt₂).

In Non Patent Literature 2 (Emmett M. Partain et al., Polymer Preprints,39, p. 82-83 (1998)), it is described that water resistance is improvedby binding cardanol having an epoxy group introduced therein tohydroxyethylcellulose.

CITATION LIST Patent Literature

-   Patent Literature 1: JP11-255801A-   Patent Literature 2: JP10-8035A-   Patent Literature 3: JP2001-32869A

Non Patent Literature

-   Non Patent Literature 1: George John et al., Polymer Bulletin,    22, p. 89-94 (1989)-   Non Patent Literature 2: Emmett M. Partain et al., Polymer    Preprints, 39, p. 82-83 (1998)

SUMMARY OF INVENTION Technical Problem

Cellulose bioplastic, whose properties are influenced by inherentproperties of cellulose, is insufficient in strength, heat resistance,water resistance and thermoplasticity. These properties need to beimproved particularly when cellulose bioplastic is applied to durableproducts such as packaging for electronic devices.

Cellulose bioplastic has the following problems. When a plasticizer isadded in order to improve thermoplasticity, heat resistance and strength(in particular, rigidity) decrease and uniformity decreases and bleedout of a plasticizer (a plasticizer bleeds out in the surface of amolded product) occurs. Furthermore, when a plasticizer formed of apetroleum feedstock is added in a large amount, the ratio of plantutilization (vegetism) decreases.

An object of the present invention is to provide a cellulose resinimproved not only in thermoplasticity (moldability), heat resistance,strength and water resistance but also in lightness of color and havinghigh vegetism and a high ratio of a non-edible part utilization, and toprovide a method for easily producing the resin.

Solution to Problem

According to an aspect of the present invention, there is provided acellulose resin produced by binding a hydrogenated cardanol including3-pentadecylcyclohexanol, and cellulose or a derivative thereof througha reaction between a hydroxy group of the hydrogenated cardanol, ahydroxy group of the cellulose or a derivative thereof and isocyanategroups of a diisocyanate compound.

According to another aspect of the present invention, there is provideda resin composition containing the aforementioned cellulose resin as abase resin.

According to another aspect of the present invention, there is provideda molding material containing the aforementioned cellulose resin as abase resin.

According to another aspect of the present invention, there is provideda method for producing a cellulose resin, including:

binding a hydrogenated cardanol including 3-pentadecylcyclohexanol, anda diisocyanate compound by reacting a hydroxy group of the hydrogenatedcardanol and an isocyanate group of the diisocyanate compound to form adiisocyanate-added cardanol derivative, and

binding the diisocyanate-added cardanol derivative and cellulose or aderivative thereof by reacting an isocyanate group of thediisocyanate-added cardanol derivative and a hydroxy group of thecellulose or a derivative thereof.

Advantageous Effects of Invention

According to an exemplary embodiment of the present invention, there isprovided a cellulose resin improved not only in thermoplasticity(moldability), heat resistance, strength and water resistance but alsoin lightness of color and having high vegetism and a high ratio of anon-edible part utilization, and provided a method for easily producingthe resin.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a process chart of a cellulose resin according to Examples ofthe present invention.

FIG. 2 is a process chart of a cellulose resin according to ReferenceExamples.

DESCRIPTION OF EMBODIMENTS

A cellulose resin according to an exemplary embodiment of the presentinvention is prepared by binding hydrogenated cardanol(3-pentadecylcyclohexanol) to cellulose or a derivative thereof by useof a diisocyanate compound. Hereinafter, binding (addition) of cardanolor a derivative thereof to cellulose or a derivative thereof isappropriately referred to as “grafting”.

In the cellulose resin, the hydroxy group of the hydrogenated cardanoland one of the isocyanate groups of a diisocyanate compound are reactedand bound, and the other isocyanate group and a hydroxy group ofcellulose or a derivative thereof are reacted to bound.

Owing to such grafting, mechanical characteristics (particularlytoughness), water resistance and lightness of color can be improved.Furthermore, since good thermoplasticity is provided by the grafting,the amount of plasticizer to be added can be reduced or a plasticizermay not be added. As a result, heat resistance and strength(particularly rigidity) can be suppressed from reducing compared to thecellulose resin containing a plasticizer, and homogeneity of theresultant resin can be improved. In addition, a problem of bleed out canbe overcome. Furthermore, since the addition amount of plasticizer madeof a petroleum feedstock can be lowered or reduced to zero, the ratio ofplant utilization can be increased. In addition, since cellulose andcardanol are both derived from a non-edible part of a plant, utilizationof a non-edible part can be enhanced.

Furthermore, in grafting hydrogenated cardanol(3-pentadecylcyclohexanol) to cellulose or a derivative thereof, use ofa diisocyanate compound enables to easily produce a grafted celluloseresin.

In the cellulose resin according to an exemplary embodiment of thepresent invention, the number DS_(CD) of hydrogenated cardanol moleculesto be added per glucose unit is preferably 0.1 or more.

Furthermore, the number of remaining hydroxy groups per glucose unit,DS_(OH), is preferably 0.9 or less.

To a hydroxy group of cellulose or a derivative thereof, a reactivehydrocarbon compound having a functional group capable of reacting withthe hydroxy group can be added. As the reactive hydrocarbon compound,compounds having a carboxyl group, a carboxylic halide group, acarboxylic acid anhydride group and an isocyanate group can be used. Asthe reactive hydrocarbon compound, an aliphatic monocarboxylic acid, anaromatic monocarboxylic acid, alicyclic monocarboxylic acid, each of theacid halides or acid anhydrides of these monocarboxylic acids, analiphatic monoisocyanate, an aromatic monoisocyanate and an alicyclicmonoisocyanate can be used. The number DS_(XX) of the reactivehydrocarbon compounds to be added per glucose unit can be set at 0.1 ormore.

Furthermore, at least one type of acyl group selected from an acetylgroup, a propionyl group and a butyryl group can be added to a hydroxygroup of cellulose or a derivative thereof. The number DS_(AC) of theacyl groups to be added per glucose unit can be set at 0.5 or more.

Furthermore, at least one type of first acyl group selected from anacetyl group, a propionyl group and a butyryl group and at least onetype of second acyl group derived from a monocarboxylic acid selectedfrom an aromatic carboxylic acid and an alicyclic carboxylic acid can beadded to a hydroxy group of cellulose or a derivative thereof. Thenumber of the first acyl group to be added per glucose unit, DS_(AC),can be set at 0.5 or more and the number of the second acyl group to beadded per glucose unit, DS_(XX), can be set at 0.1 or more.

Furthermore, the total amount of cellulose component and cardanolcomponent is preferably 50% by mass or more based on the whole resin.

The resin composition according to an exemplary embodiment of thepresent invention contains a cellulose resin as a base resin and canfurther contain a thermoplastic polyurethane elastomer or a modifiedsilicone compound.

[Cellulose or a Derivative Thereof]

Cellulose is a straight-chain polymer of β-glucose, represented by thefollowing formula (1) and each glucose unit has three hydroxy groups.Using these hydroxy groups, a cardanol derivative can be grafted.

Cellulose is a main component of a plant and can be obtained by aseparation treatment for removing other components such as lignin from aplant. Other than the cellulose thus obtained, cellulose obtained bypurification of cotton or pulp rich in cellulose content can be used, orthe cotton or pulp can be directly used.

The polymerization degree of cellulose (or a derivative thereof)preferably falls within the range of 50 to 5000 and more preferably 100to 3000 in terms of glucose polymerization degree. If the polymerizationdegree is extremely low, the strength and heat resistance of theproduced resin may not be sufficient in some cases. Conversely, if thepolymerization degree is extremely high, the melt viscosity of theproduced resin is extremely high, interfering with molding in somecases.

Cellulose (or a derivative thereof) may be mixed with chitin andchitosan having an analogous structure. When cellulose is mixed withthem, the amount thereof is preferably 30% by mass or less relative tothe total amount of mixture, preferably 20% by mass or less and furtherpreferably 10% by mass or less.

A cellulose derivative herein refers to cellulose having hydroxy groupspartly acylated, etherified or grafted. Specific examples thereofinclude organic acid esters such as cellulose acetate, cellulosebutyrate and cellulose propionate; inorganic acid esters such ascellulose nitrate, cellulose sulfate and cellulose phosphate; mixedesters such as cellulose acetate propionate, cellulose acetate butyrate,cellulose acetate phthalate and cellulose acetate nitrate; andetherified cellulose such as methylcellulose, hydroxyethylcellulose andhydroxypropylcellulose. Furthermore, celluloses grafted with styrene,(meth)acrylic acid, (meth)acrylate, ε-caprolactone, lactide, glycolide,etc. These acylated cellulose, etherified cellulose and graftedcellulose may be used singly or in combination of two or more types.

As the cellulose (or a derivative thereof) of the exemplary embodiment,for example, at least one acylated cellulose selected from a celluloseacetate, cellulose propionate and cellulose butyrate which have a partof the hydroxy groups acylated can be preferably used.

The term “cellulose derivative” used herein includes both a cellulosecompound and a compound having a cellulose skeleton obtained bybiologically or chemically introducing a functional group intoraw-material cellulose.

[Grafting of Hydrogenated Cardanol (3-pentadecylcyclohexanol)]

Hydrogenated cardanol (3-pentadecylcyclohexanol) is obtained fromcardanol, which is a component contained in the shell of cashew nut.Cardanol is an organic compound having a phenol moiety and astraight-chain hydrocarbon moiety and represented by the followingformula (2). There are 4 types of cardanols different in the number ofunsaturated bonds in the straight-chain hydrocarbon moiety R. Usually,cardanol is a mixture of these 4 components. To be more specific,cardanol is a mixture of 3-pentadecylphenol, 3-pentadecylphenol monoene,3-pentadecylphenol diene and 3-pentadecylphenol triene, described in thefollowing formula (2). Cardanol obtained by extracting and purifyingfrom a cashew nutshell liquid can be used.

The straight-chain hydrocarbon moiety of cardanol contributes toimproving flexibility and hydrophobicity of a resin, whereas the phenolmoiety has a highly reactive hydroxy group for use in grafting. Whenhydrogenated cardanol (3-pentadecylcyclohexanol) obtained from suchcardanol is grafted to cellulose (or a derivative thereof), a cellulosestructure to which hydrogenated cardanol (3-pentadecylcyclohexanol) isadded like bristles is formed. As a result, hydrogenated cardanolbristles thus grafted interact with each other to improve mechanicalcharacteristics (particularly toughness), as well as to impartthermoplasticity. In addition, owing to hydrophobicity of hydrogenatedcardanol, water resistance can be improved.

Hydrogenated cardanol (3-pentadecylcyclohexanol) is obtained byconverting the unsaturated bonds (double bonds) of the phenol moiety ofthe cardanol and a straight-chain hydrocarbon moiety thereof intosaturated bonds by hydrogenation. The conversion rate (hydrogenationrate) of the unsaturated bonds by hydrogenation is preferably 90% bymole or more and more preferably 95% by mole or more. Afterhydrogenation, the residual ratio of unsaturated bonds in cardanol (thenumber of unsaturated bonds per cardanol molecule) is preferably 0.2bonds/molecule or less and more preferably 0.1 bond/molecule or less.

When hydrogenated cardanol (3-pentadecylcyclohexanol) in which a largenumber of unsaturated bonds still remain in the phenol moiety, isgrafted to cellulose (or a derivative thereof) via a diisocyanatecompound, a crosslinking decomposition reaction proceeds duringheat-welding time, with the result that thermoplasticity may disappear.When hydrogenated cardanol (3-pentadecylcyclohexanol), in whichunsaturated bonds of the phenol moiety are sufficiently converted intosaturated bonds by hydrogenation, is grafted, the crosslinkingdecomposition reaction during heat-welding time is suppressed to obtaina grafted cellulose resin having satisfactory thermoplasticity.

Furthermore, when hydrogenated cardanol (3-pentadecylcyclohexanol) inwhich a large number of unsaturated bonds still remain in thestraight-chain hydrocarbon moiety, is grafted to cellulose (or aderivative thereof), a side reaction is likely to occur, with the resultthat grafting cannot be efficiently performed and the solubility of agrafted product in a solvent may often significantly reduce. When acardanol derivative, in which an unsaturated bond(s) of thestraight-chain hydrocarbon moiety are sufficiently converted intosaturated bonds by hydrogenation, is grafted, grafting can beefficiently performed whereas a side reaction is suppressed and inaddition, reduction of solubility of a grafted product in a solvent canbe suppressed.

The hydrogenation method is not particularly limited and a method knownin the art can be used. As the catalyst, a precious metal such aspalladium, ruthenium, rhodium and platinum or nickel, or a metalselected from these immobilized on a carrier such as activated carbon,activated alumina and diatom earth is mentioned. As the reaction system,a batch system, in which a reaction is performed while suspending andstirring a powdery catalyst, and a continuous system using a reactiontower charged with a molded catalyst, can be employed. The solvent forhydrogenation may not be used depending upon the system ofhydrogenation. However, when a solvent is used, alcohols, ethers, estersand saturated hydrocarbons are generally mentioned. The reactiontemperature for hydrogenation is not particularly limited; however, itcan be usually set at 20 to 250° C. and preferably 50 to 200° C. If thereaction temperature is excessively low, a hydrogenation rate becomeslow. Conversely, if the reaction temperature is excessively high, theamount of decomposition product may increase. The hydrogen pressureduring the hydrogenation can be usually set at 10 to 80 kgf/cm² (9.8×10⁵to 78.4×10⁵ Pa) and preferably 20 to 50 kgf/cm² (19.6×10⁵ to 49.0×10⁵Pa).

Hydrogenation can be performed before a diisocyanate-added cardanolderivative is formed, after a diisocyanate-added cardanol derivative isformed and before the cardanol derivative is grafted, or after adiisocyanate-added cardanol derivative is grafted; however, in view ofthe reaction efficiency of hydrogenation and grafting reaction,hydrogenation is preferably performed before a diisocyanate-addedcardanol derivative is grafted and further preferably before adiisocyanate-added cardanol derivative is formed.

Grafting is performed by using a diisocyanate compound capable ofreacting with a hydroxy group of cellulose (or a derivative thereof) andthe hydroxy group of hydrogenated cardanol (3-pentadecylcyclohexanol).As a result, the carbon atom of cellulose to which the hydroxy group ofcellulose (or a derivative thereof) is bound and the cardanol carbonatom to which the hydroxy group of hydrogenated cardanol(3-pentadecylcyclohexanol) is bound are connected via two urethane bondslinked with an organic group (for example, an alkylene chain having 3 to12 carbon atoms). Due to such grafting, the efficiency of a graftingreaction can be improved and a side reaction can be suppressed. Inaddition, production can be made by a simple method having a fewermanufacturing steps with less amount of by-product.

For example, one of the isocyanate groups of a diisocyanate compound isbound to the hydroxy group of hydrogenated cardanol(3-pentadecylcyclohexanol) to obtain a diisocyanate-added cardanolderivative. Subsequently, the resultant diisocyanate-added cardanolderivative and cellulose (or a derivative thereof) can be bound by useof a hydroxy group of cellulose (or a derivative thereof) and theisocyanate group of the diisocyanate-added cardanol derivative.

According to the aforementioned grafting, the hydroxy group of cellulose(or a derivative thereof) and the hydroxy group of hydrogenated cardanol(3-pentadecylcyclohexanol) are eliminated to form a graft bond; at thesame time, the hydrophobic structure of cardanol can be introduced intocellulose (or a derivative thereof) to improve water resistance.

To graft hydrogenated cardanol (3-pentadecylcyclohexanol) to cellulose(or a derivative thereof), the hydroxy group of hydrogenated cardanol(3-pentadecylcyclohexanol) and a hydroxy group of cellulose arepreferably used as mentioned above in view of efficiency of a graftingreaction, resultant molecular structure and water resistance. Since suchgrafting is made by use of a highly-reactive hydroxy group, moreefficient grafting can be realized compared to grafting using anunsaturated bond (double bond) of the straight-chain hydrocarbon moietyof cardanol. Furthermore, according to the grafting of the exemplaryembodiment, since the cyclohexane moiety of hydrogenated cardanol(3-pentadecylcyclohexanol) reacts with cellulose and fixed to it,interaction between mutual straight-chain hydrocarbon moieties of thegrafted hydrogenated cardanol (3-pentadecylcyclohexanol) moleculesenhances, and thus a desired effect of improving mechanicalcharacteristics can be obtained. Furthermore, in the exemplaryembodiment, grafting is performed by eliminating the hydroxy group of acardanol derivative, water resistance can be improved (suppressing waterabsorbability) compared to grafting that does not use a hydroxy group.Also from this point of view, the grafting of the exemplary embodimentis advantageous.

The aforementioned diisocyanate compound is preferably a compoundcontaining a hydrocarbon group to which two isocyanate groups are bound.The number of carbon atoms of the hydrocarbon group is preferably 3 ormore and also preferably 20 or less and preferably 15 or less andfurther preferably 12 or less. If the number of carbon atoms isexcessively large, the molecule becomes excessively large and thusreactivity reduces. As a result, it is often difficult to increase agrafting rate.

Examples of such a hydrocargon group include a divalent straight-chainaliphatic hydrocarbon groups (particularly, straight-chain alkylenegroup) such as a methylene group, an ethylene group, a propylene group,a butylene group, a pentamethylene group, a hexamethylene group, aheptamethylene group, an octamethylene group, a decamethylene group, adodecamethylene group and a hexadecamethylene group; divalent alicyclichydrocarbon groups having the free valence on a carbon atom of aaliphatic ring such as a cycloheptane ring, a cyclohexane ring, acyclooctane ring, a bicyclopentane ring, a tricyclohexane ring, abicyclooctane ring, a bicyclononane ring and a tricyclodecane ring;divalent aromatic hydrocarbon groups (phenylene group, naphthylenegroup, biphenylene group and the like) having the free valence on acarbon atom of an aromatic ring such as a benzene ring and a naphthalenering; and divalent groups composed of combinations of these.

When a hydrocarbon group as mentioned above is an aromatic hydrocarbongroup or an alicyclic hydrocarbon group, because of its stiffness, therigidity of the resultant resin can be improved. In contrast, when theaforementioned hydrocarbon group is a straight-chain aliphatichydrocarbon group, because of its flexibility, the toughness of theresultant resin can be improved. In particular, an aliphaticdiisocyanate having a straight-chain alkylene chain having 3 to 12carbon atoms to both ends of which an isocyanate group is bound ispreferable.

Specific examples of such a diisocyanate compound include aliphaticdiisocyanate compounds such as 1,3-trimethylene diisocyanate,1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI),1,8-octamethylene diisocyanate and 1,12-dodecamethylene diisocyanate;aromatic diisocyanate compounds such as tolylene diisocyanate (TDI),4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate(NDI), tolidine diisocyanate, xylene diisocyanate (XDI) andtetramethylxylene diisocyanate (TMXDI); and alicyclic diisocyanatecompounds such as dicyclohexylmethane diisocyanate (HMDI: hydrogenatedMDI), hydrogenated XDI and isophorone diisocyanate (IPDI). Of these,1,6-hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI) and4,4′-diphenylmethane diisocyanate (MDI) can be preferably used.

An isocyanate group of a diisocyanate compound as mentioned above andthe hydroxy group of a cardanol derivative are reacted to form adiisocyanate-added cardanol derivative, and then, the diisocyanate-addedcardanol derivative is bound to cellulose (or a derivative thereof) byreacting a hydroxy group of cellulose (or a derivative thereof) and theisocyanate group of the diisocyanate-added cardanol derivative.

In a method for performing grafting by use of such a diisocyanatecompound, a cellulose resin can be more easily produced with a fewerreaction steps without producing by-products, compared to a method inwhich a carboxylic multifunctional compound (dicarboxylic acid,carboxylic acid anhydride or monochloro acetic acid) is reacted withcardanol to prepare a cardanol derivative having a carboxyl group andthe carboxylic acid group of the derivative is allowed to bind to thehydroxy group of cellulose (or a derivative thereof).

The ratio (grafting rate) of hydrogenated cardanol bound to cellulose(or a derivative thereof) relative to the cellulose (or a derivativethereof) is represented by the number (DS_(CD)) (average value) ofhydrogenated cardanol molecules to be added per glucose unit ofcellulose (or a derivative thereof), in other words, the number ofhydroxy groups bound to hydrogenated cardanol molecules (the degree ofsubstitution of the hydroxy group) (average value). DS_(CD) ispreferably 0.1 or more and more preferably 0.2 or more. DS_(CD) may beset to 0.4 or more. When DS_(CD) is excessively low, the effect bygrafting may not be sufficiently obtained.

The maximum value of DS_(CD) is theoretically “3”; however, in view offacilitating production (grafting), DS_(CD) is preferably 2.5 or less,more preferably 2 or less and further preferably 1.5 or less.Furthermore, DS_(CD) may be 1 or less. Even in this case, sufficientimprovement effect can be obtained. If DS_(CD) increases, tensilebreaking strain (toughness) increases; whereas, the maximum strength(tensile strength, bending strength) tends to decrease. Therefore,DS_(CD) is preferably set appropriately in accordance with desiredproperties.

[Grafting of Reactive Hydrocarbon Compounds]

Hydrogenated cardanol is grafted and simultaneously, a specific reactivehydrocarbon compound may be grafted to cellulose (or a derivativethereof). Owing to this, a cellulose resin can be improved so as to havedesired properties.

This reactive hydrocarbon compound is a compound having at least onefunctional group capable of reacting with a hydroxy group of cellulose(or a derivative thereof). Examples thereof include hydrocarboncompounds having a carboxyl group, a carboxylic halide group, acarboxylic acid anhydride group, an isocyanate group, a chloroformategroup or an acryl group. Specific examples thereof include at least onecompound selected from monocarboxylic acids such as an aliphaticmonocarboxylic acid, an aromatic monocarboxylic acid and an alicyclicmonocarboxylic acid, and acid halides or acid anhydrides thereof; atleast one compound selected from an aliphatic monoisocyanate, anaromatic monoisocyanate and an alicyclic monoisocyanate; at least onecompound selected from an aliphatic monochloroformate, an aromaticmonochloroformate and an alicyclic monochloroformate; an acrylic acidester; and a methacrylic acid ester.

As the aliphatic monocarboxylic acid, a straight or branched (having aside chain) fatty acid is mentioned. Examples of the aromaticmonocarboxylic acid include an aromatic monocarboxylic acid having acarboxyl group directly bound to an aromatic ring and an aromaticmonocarboxylic acid having a carboxyl group bound to the aromatic ringvia an alkylene group (for example, methylene group, ethylene group)(the acid having an aliphatic carboxylic acid group bound to thearomatic ring). Examples of the alicyclic monocarboxylic acid include analicyclic monocarboxylic acid having a carboxyl group directly bound toan alicycle and an alicyclic monocarboxylic acid having a carboxyl groupbound to an alicycle (an aliphatic carboxylic acid group bound to thealicycle) via an alkylene group (for example, methylene group, ethylenegroup)(the acid having an aliphatic carboxylic acid group bound to analicycle).

Examples of the aliphatic monoisocyanate include an aliphaticmonoisocyanate having an isocyanate group bound to a straight aliphatichydrocarbon or a branched aliphatic hydrocarbon having a side chain.Examples of the aromatic monoisocyanate include an aromaticmonoisocyanate having an isocyanate group directly bound to an aromaticring and an aromatic monoisocyanate having an isocyanate group bound toan aromatic ring via an alkylene group (for example, a methylene groupor an ethylene group) (the aromatic monoisocyanate having an aliphaticisocyanate group bound to an aromatic ring). Examples of the alicyclicmonoisocyanate include an alicyclic monoisocyanate having an isocyanategroup directly bound to an alicycle and an alicyclic monoisocyanatehaving an isocyanate group bound to an alicycle via an alkylene group(for example, a methylene group or an ethylene group) (the alicyclicmonoisocyanate having an aliphatic isocyanate group bound to analicycle).

Examples of the aliphatic monochloroformate include an aliphaticmonochloroformate having a chloroformate group bound to a straightaliphatic hydrocarbon or a branched aliphatic hydrocarbon having a sidechain. Examples of the aromatic monochloroformate include an aromaticmonochloroformate having a chloroformate group directly bound to anaromatic ring and an aromatic monochloroformate having a chloroformategroup bound to an aromatic ring via an alkylene group (for example, amethylene group or an ethylene group) (the aromatic monochloroformatehaving an aliphatic chloroformate group bound to an aromatic ring).Examples of the alicyclic monochloroformate include an alicyclicmonochloroformate having a chloroformate group directly bound to analicycle and an alicyclic monochloroformate having a chloroformate groupbound to an alicycle via an alkylene group (for example, a methylenegroup or an ethylene group) (the alicyclic monochloroformate having analiphatic chloroformate group bound to an alicycle).

The reactive hydrocarbon compound preferably has carbon atoms within therange of 1 to 32 and more preferably within the range of 1 to 20. If thenumber of carbon atoms is excessively large, the size of the moleculebecomes excessively large and reaction efficiency decreases due tosteric hindrance. As a result, it becomes difficult to increase agrafting rate.

The reactive hydrocarbon compound is effective in improving propertiesin the case where it is particularly arranged so as to bury gaps in asterical structure composed of grafted hydrogenated cardanols.

When the hydrocarbon group of the reactive hydrocarbon compound is anaromatic hydrocarbon group and an alicyclic hydrocarbon group, itefficiently works to particularly improve rigidity and heat resistance.When the hydrocarbon group is an aliphatic hydrocarbon group, itefficiently works to particularly improve toughness.

Examples of the aliphatic monocarboxylic acid to be used as the reactivehydrocarbon compound include saturated fatty acids such as acetic acid,propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid,caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylicacid, undecylic acid, lauric acid, tridecylic acid, myristic acid,pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid,nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, ceroticacid, heptacosanoic acid, montanic acid, melissic acid and laccericacid; unsaturated fatty acids such as butenoic acid, pentenoic acid,hexenoic acid, octenoic acid, undecylenic acid, oleic acid, sorbic acid,linoleic acid, linolenic acid and arachidonic acid; and derivatives ofthese. These may further have a substituent.

Examples of the aromatic monocarboxylic acid used as the reactivehydrocarbon compound include an aromatic carboxylic acid having acarboxyl group introduced in a benzene ring such as benzoic acid; anaromatic carboxylic acid having an alkyl group introduced in a benzenering such as toluic acid; an aromatic carboxylic acid having analiphatic carboxylic acid group introduced in a benzene ring such asphenylacetic acid and phenyl propionic acid; an aromatic carboxylic acidhaving two or more benzene rings such as biphenylcarboxylic acid andbiphenylacetic acid; an aromatic carboxylic acid having a condensed-ringstructure such as naphthalene carboxylic acid and tetralin carboxylicacid; and derivatives of these.

Examples of the alicyclic monocarboxylic acid to be used as the reactivehydrocarbon compound include an alicyclic monocarboxylic acid having acarboxyl group introduced to an alicycle such as cyclopentane carboxylicacid, cyclohexane carboxylic acid and cyclooctane carboxylic acid;alicyclic monocarboxylic acids having an aliphatic carboxylic acidintroduced in an alicycle such as cyclohexyl acetic acid; andderivatives of these.

Examples of the aliphatic monoisocyanate used as the reactivehydrocarbon compound include saturated aliphatic isocyanates such asmethyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropylisocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate,heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate,dodecyl isocyanate and octadecyl isocyanate; unsaturated aliphaticisocyanates such as butenyl isocyanate, pentenyl isocyanate, hexenylisocyanate, octenyl isocyanate and dodecenyl isocyanate; and derivativesof these. These may further have a substituent.

Examples of the aromatic monoisocyanate used as the reactive hydrocarboncompound include an aromatic monoisocyanate having an isocyanate groupintroduced in a benzene ring, such as phenyl isocyanate; an aromaticcarboxylic acid having an alkyl group introduced in a benzene ring, suchas tolyl isocyanate; an aromatic monoisocyanate having an aliphaticisocyanate group introduced in a benzene ring, such as phenylmethylisocyanate and phenylethyl isocyanate; an aromatic isocyanate having twoor more benzene rings, such as biphenyl isocyanate and biphenyl methylisocyanate; aromatic isocyanate having a condensation ring structure,such as naphthaline isocyanate and tetralin isocyanate; and derivativesof these.

Examples of the alicyclic monoisocyanate used as the reactivehydrocarbon compound include an alicyclic monoisocyanate having anisocyanate group introduced in an alicycle, such as cyclopentylisocyanate, cyclohexyl isocyanate and cyclooctyl isocyanate; analicyclic monoisocyanate having an aliphatic isocyanate group introducedin an alicycle, such as cyclohexylmethyl isocyanate; and derivatives ofthese.

Examples of the aliphatic monochloroformate used as the reactivehydrocarbon compound include saturated aliphatic chloroformates such asmethyl chloroformate, ethyl chloroformate, propyl chloroformate,isopropyl chloroformate, butyl chloroformate, pentyl chloroformate,hexyl chloroformate, heptyl chloroformate, octyl chloroformate, nonylchloroformate, decyl chloroformate, dodecyl chloroformate and octadecylchloroformate; unsaturated aliphatic chloroformates such as butenylchloroformate, pentenyl chloroformate, hexenyl chloroformate, octenylchloroformate and dodecenyl chloroformate; and derivatives of these.These may further have a substituent.

Examples of the aromatic monochloroformate used as the reactivehydrocarbon compound include an aromatic monochloroformate having achloroformate group introduced in a benzene ring, such as phenylchloroformate; an aromatic carboxylic acid having an alkyl groupintroduced in a benzene ring, such as tolyl chloroformate; an aromaticmonochloroformate having an aliphatic chloroformate group introduced ina benzene ring, such as phenylmethyl chloroformate and phenylethylchloroformate; an aromatic chloroformate having two or more benzenerings, such as biphenyl chloroformate and biphenylmethyl chloroformate;an aromatic chloroformate having a condensation ring structure such asnaphthaline chloroformate and tetralin chloroformate; and derivatives ofthese.

Examples of the alicyclic monochloroformate used as the reactivehydrocarbon compound include an alicyclic monochloroformate having achloroformate group introduced in an alicycle, such as cyclopentylchloroformate, cyclohexyl chloroformate and cyclooctyl chloroformate; analicyclic monochloroformate having an aliphatic chloroformate groupintroduced in an alicycle such as cyclohexylmethyl chloroformate; andderivatives of these.

If an organic silicon compound and an organic fluorine compound areadded to these reactive hydrocarbon compound structures, properties suchas water resistance can be more effectively improved.

As the reactive functional groups of these reactive hydrocarboncompounds, any reactive functional groups are used as long as they canreact with a hydroxy group of cellulose. Examples thereof include acarboxyl group, a carboxylic acid halide group (particularly, acarboxylic acid chloride group), a carboxylic acid anhydride, anisocyanate group, a chloroformate group and further include an epoxygroup and a halogen group (particularly, a chloride group). Of these, acarboxyl group, a carboxylic acid halide group, an isocyanate group anda chloroformate group are preferable, and a carboxylic acid chloridegroup, an isocyanate group and a chloroformate group are particularlypreferable. As the carboxylic acid halide group (particularly, acarboxylic acid chloride group), an acid halide group (particularly, anacid chloride group) in which a carboxyl group of each of the carboxylicacids mentioned above is acid-halogenated, is mentioned.

As the reactive hydrocarbon compound used in the exemplary embodiment,particularly in view of rigidity (bending strength, etc.) of a resin, atleast one monocarboxylic acid selected from aromatic carboxylic acidsand alicyclic carboxylic acids, an acid halide or acid anhydridethereof, aromatic monoisocyanate, aliphatic monoisocyanate, aromaticmonochloroformate and aliphatic monochloroformate are preferable. Byadding such a reactive hydrocarbon compound to a hydroxy group ofcellulose, a structure in which an acyl group derived from at least onetype of monocarboxylic acid selected from aromatic carboxylic acids andalicyclic carboxylic acids, a carbamoyl group derived from at least onetype of monoisocyanate selected from aromatic monoisocyanates andalicyclic monoisocyanates, or a carbonate group derived from at leastone type of chloroformate selected from aromatic monochloroformates andalicyclic monochloroformates is added to the hydroxy group of cellulose,(more specifically, the structure formed by substituting the hydrogenatom of a hydroxy group of cellulose with an acyl group, a carbamoylgroup or a carbonate group) can be obtained.

The number (average value) of reactive hydrocarbon compounds (the numberof acyl groups, carbamoyl groups or carbonate groups, DS_(XX)) to beadded per glucose unit of cellulose (or a derivative thereof), in otherwords, the number of hydroxy groups bound to a reactive hydrocarboncompound (the degree of substitution of the hydroxy group) (averagevalue) is, in view of obtaining a desired effect, preferably 0.1 or moreand 0.6 or less and more preferably 0.1 or more and 0.5 or less.

Furthermore, after hydrogenated cardanol and a reactive hydrocarboncompound are grafted, the number of remaining hydroxy groups per glucoseunit (hydroxy group remaining degree, DS_(OH)) (average value) is, inview of sufficiently ensuring water resistance and resistance to thermaldecomposition, preferably 0.9 or less and more preferably, 0.7 or less.

The reactive hydrocarbon compound can be grafted in the grafting step ofhydrogenated cardanol. Owing to this, grafting can be made uniformly. Atthis time, these may be added simultaneously or separately. However, ifhydrogenated cardanol is grafted and thereafter a reactive hydrocarboncompound is added and grafted, the efficiency of a grafting reaction canbe improved.

[Grafting Treatment]

A grafting treatment can be performed by heating cellulose (or aderivative thereof) and hydrogenated cardanol, if necessary, a reactivehydrocarbon compound in a solvent dissolving them, with a catalyst ifnecessary, at an appropriate temperature. Cellulose is rarely dissolvedin a general solvent; however dissolved in e.g., adimethylsulfoxide-amine solvent, a dimethylformamide-chloral-pyridinesolvent, a dimethylacetamide-lithium chloride solvent and an imidazoliumionic liquid. When a grafting reaction is performed in a generalsolvent, a cellulose derivative, the solubility of which has beenchanged by previously binding a carboxylic acid and an alcohol to a partof hydroxy groups of cellulose to reduce intermolecular force, can beused. Acylated cellulose having a hydroxy group whose hydrogen atom issubstituted with an acyl group such as an acetyl group, a propionylgroup and a butyryl group is preferable. In particular, celluloseacetate, which is an acetylated cellulose with acetic acid or acetylchloride is preferable. Acetic acid, propionic acid, butyric acid and anacid halide and acid anhydride thereof are included in theaforementioned reactive hydrocarbon compounds; however, like thisexample, whole or part of predetermined reactive hydrocarbon compoundscan be added (grafted) to a hydroxy group of cellulose before graftingwith hydrogenated cardanol.

When grafting treatment is performed by use of the acylated cellulose,the solvent to be selected preferably has a polarity value of (RelativePolarity) of 0.15 or more and 0.5 or less. Examples of the solventsatisfying the range include dioxane, tetrahydrofuran, ethyl acetate,chloroform, pyridine, methyl ethyl ketone, acetone, dimethylformamideand dimethylsulfoxide. These solvents may be used alone or as a mixtureof two or more types. In the cases where a polarity value is less than0.15 and larger than 0.5, the solubilities of acylated cellulose and acellulose resin resulting from grafting treatment are low, with theresult that reaction efficiency may significantly reduce. The polarityvalue refers to a value indicating how higher polarity the solvent hasrelative to water (polarity is 1) and defined in Solvents and SolventEffects in Organic Chemistry, Wiley-VCH Publishers, 2rd ed., 1988, pp359-373. Furthermore, when a solvent having a polarity value within therange and a specific gravity of 0.95 or less is used, the removalefficiency of impurities remaining in a product by filtration increases,with the result that a cellulose resin can be more easily produced.Examples of such a solvent include tetrahydrofuran, ethyl acetate,methyl ethyl ketone, acetone and dimethylformamide. These solvents maybe used alone or as a mixture of two or more types.

When a catalyst is used in grafting treatment, if a catalyst inactivatoris added, the remaining catalyst in a cellulose resin is inactivated,thereby improving e.g., stability against heat. As a means forinactivating a catalyst, adding an inactivator such as phosphoric acid,and adding a catalyst adsorbent such as porous silica are mentioned.

[Remaining Amount of Hydroxy Group]

The remaining hydroxy group that is not used in grafting hydrogenatedcardanol is a hydroxy group without being modified, a modified hydroxygroup by acetylation, or a hydroxy group to which a reactive hydrocarboncompound is added (grafted). As the amount of hydroxy group increases,maximum strength and heat resistance tend to increase; whereas waterabsorbability tends to increase. As the conversion rate (degree ofsubstitution) of hydroxy groups increases, water absorbability tends todecrease, plasticity and breaking strain tend to increase; whereas,maximum strength and heat resistance tend to decrease. In considerationof these tendencies and grafting conditions, the conversion rate ofhydroxy groups can be appropriately set.

In view of ensuring sufficient water resistance, the number of remaininghydroxy groups of a cellulose resin grafted per glucose unit (hydroxygroup remaining degree, DS_(OH)) (average value) is preferably 0.9 orless and more preferably 0.7 or less.

[Degree of Substitution of Hydroxyl Groups by Acylation]

In view of water absorbability, mechanical strength and heat resistance,it is preferred that the hydroxy groups of cellulose are partly acylatedwith a reactive hydrocarbon as mentioned above. Furthermore, in view ofthe aforementioned grafting treatment of hydrogenated cardanol, it ispreferred that hydroxy groups of cellulose are appropriately acylated(particularly, acetylated) before grafting of hydrogenated cardanol. Thenumber of acyl groups (DS_(AC)) (average value) to be added per glucoseunit of cellulose (or a derivative thereof), in other words, the numberof hydroxy groups acylated (degree of substitution of hydroxy groups)(average value) is preferably 0.5 or more in view of obtainingsufficient acylation effect, more preferably 1.0 or more, and furtherpreferably 1.5 or more. Furthermore, in view of ensuring the sufficientgrafting rate (DS_(CD)) of hydrogenated cardanol, the degree ofsubstitution of hydroxy groups, DS_(AC) by acylation is preferably 2.7or less, more preferably 2.5 or less and further preferably 2.2 or less.The acyl group to be added by acylation is preferably at least one acylgroup selected from an acetyl group, a propionyl group and a butyrylgroup. Note that the degree of substitution by acetylation isrepresented by DS_(Ace), the degree of substitution by propionation isrepresented by DS_(Pr), and the degree of substitution by butylation isrepresented by DS_(Bu).

[Plant Component Ratio]

In the cellulose resin according to the exemplary embodiment, in view ofensuring a sufficient plant utilization ratio, the mass ratio of the sumof a cellulose component and a cardanol component relative to the totalcellulose resin after grafting (plant component ratio) is preferably 50%or more and more preferably 60% or more. Herein, the cellulose componentcorresponds to the structure represented by Formula (1) where thehydroxy groups are not acylated or grafted, whereas the cardanolcomponent corresponds to the structure represented by Formula (2). Onthe assumption of these, calculation is made.

[Additives]

To the cellulose resin according to the exemplary embodiment describedabove, various types of additives usually used in thermoplastic resinscan be applied. For example, if a plasticizer is added, thermoplasticityand breaking elongation can be more improved. Examples of such aplasticizer include phthalic esters such as dibutyl phthalate, diarylphthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethylphthalate, ethyl phthalyl ethyl glycolate and methyl phthalyl ethylglycolate; tartaric acid esters such as dibutyl tartrate; adipic acidesters such as dioctyl adipate and diisononyl adipate; polyhydricalcohol esters such as triacetin, diacetyl glycerin, tripropionitrileglycerin and glyceryl monostearate; phosphoric acid esters such astriethyl phosphate, triphenyl phosphate and tricresyl phosphate; dibasicfatty acid esters such as dibutyl adipate, dioctyl adipate, dibutylazelate, dioctyl azelate and dioctyl sebacate; citric acid esters suchas triethyl citrate, acetyltriethyl citrate and tributyl acetylcitrate;epoxylated vegetable oils such as epoxylated soybean oil and epoxylatedlinseed oil; castor oil and a derivative thereof; benzoic acid esterssuch as ethyl O-benzoyl benzoate; aliphatic dicarboxylic acid esterssuch as sebacate and azelate; unsaturated dicarboxylic acid esters suchas maleate; and N-ethyl toluene sulfonamide, triacetin, O-cresylp-toluenesulfonate and tripropionin Of them, particularly, if aplasticizer such as dioctyl adipate, benzyl-2butoxyethoxyethyl adipate,tricresyl phosphate, diphenylcresyl phosphate and diphenyloctylphosphate is added, not only thermoplasticity and elongation duringbreakage but also impact resistance can be effectively improved.

Examples of other plasticizers include cyclohexane dicarboxylic acidesters such as dihexyl cyclohexanedicarboxylate, dioctylcyclohexanedicarboxylate and di-2-methyloctyl cyclohexanedicarboxylate;trimellitic acid esters such as dihexyl trimellitate, diethylhexyltrimellitate and dioctyl trimellitate; and pyromellitic acid esters suchas dihexyl pyromellitate, diethylhexyl pyromellitate and dioctylpyromellitate.

The reactive functional group (a carboxylic acid group, a group derivedfrom a carboxylic acid group, other functional groups) of such aplasticizer may be reacted with a hydroxy group or an unsaturated bondof cardanol to allow cardanol to add to a plasticizer. If such aplasticizer is used, compatibility of the cellulose resin of theexemplary embodiment and the plasticizer can be improved. Therefore, theaddition effect of the plasticizer can be more improved.

To the cellulose resin of the exemplary embodiment, if necessary, aninorganic or organic granular or fibrous filler can be added. By addinga filler, strength and rigidity can be more improved. Examples of thefiller include, mineral particles (talc, mica, baked siliceous earth,kaolin, sericite, bentonite, smectite, clay, silica, quartz powder,glass beads, glass powder, glass flake, milled fiber, Wollastonite,etc.), boron-containing compounds (boron nitride, boron carbonate,titanium boride etc.), metal carbonates (magnesium carbonate, heavycalcium carbonate, light calcium carbonate, etc.), metal silicates(calcium silicate, aluminum silicate, magnesium silicate, magnesiumaluminosilicate, etc.), metal oxides (magnesium oxide etc.), metalhydroxides (aluminum hydroxide, calcium hydroxide, magnesium hydroxide,etc.), metal sulfates (calcium sulfate, barium sulfate, etc.), metalcarbides (silicon carbide, aluminum carbide, titanium carbide, etc.),metal nitrides (aluminum nitride, silicon nitride, titanium nitride,etc.), white carbon and metal foils. Examples of the fibrous fillerinclude organic fibers (natural fiber, papers etc.), inorganic fibers(glass fiber, asbestos fiber, carbon fiber, silica fiber, silica aluminafiber, Wollastonite, zirconia fiber, potassium titanate fiber etc.) andmetal fibers. These fillers can be used singly or in combination of twoor more types.

To the cellulose resin of the exemplary embodiment, if necessary, aflame retardant can be added. By adding a flame retardant, flameresistance can be imparted. Examples of the flame retardant includemagnesium hydroxide, aluminum hydroxide, metal hydrates such ashydrotalcite, basic magnesium carbonate, calcium carbonate, silica,alumina, talc, clay, zeolite, bromine-based flame retardant, antimonytrioxide, phosphoric acid based flame retardant (aromatic phosphate,aromatic condensed phosphate, etc.), compounds containing phosphorus andnitrogen (phosphazene compound), etc. These flame retardants can be usedsingly or in combination with two or more types.

Furthermore, as the flame retardant, a reaction product between aphosphorus oxide, a phosphoric acid or a derivative of each of these andcardanol, and a polymer of the reaction product can be used. If such aflame retardant is used, the interaction between the cellulose resin ofthe exemplary embodiment and a flame retardant is enhanced, excellentflame-retardant effect can be obtained. Examples of such a flameretardant include a reaction product between phosphorus oxide (P₂O₅) orphosphoric acid (H₃PO₄) and a hydroxy group of cardanol, and a polymerobtained by adding hexamethylene tetramine to the reaction product,followed by polymerizing.

To the cellulose resin of the exemplary embodiment, if necessary, animpact resistance improver can be added. By adding a impact resistanceimprover, impact resistance can be improved. Examples of the impactresistance improver include a rubber component and a silicone compound.Examples of the rubber component include a natural rubber, epoxylatednatural rubber and synthesized rubber. Furthermore, examples of thesilicone compound include organic polysiloxane formed by polymerizationof alkyl siloxane, alkyl phenyl siloxane, etc., and modified siliconecompounds obtained by modifying a side chain or an end of an organicpolysiloxane as mentioned above with polyether, methylstyryl, alkyl,higher fatty acid ester, alkoxy, fluorine, an amino group, an epoxygroup, a carboxyl group, a carbinol group, a methacryl group, a mercaptogroup, a phenol group etc. These impact resistance improvers can be usedsingly or in combination of two or more types.

As the silicone compound, a modified silicone compound (modifiedpolysiloxane compound) is preferred. As the modified silicone compound,a modified polydimethyl siloxane is preferred, which has a structurehaving a main chain constituted of dimethyl siloxane repeat units and aside chain or a terminal methyl group partly substituted with an organicsubstituent containing at least one group selected from an amino group,an epoxy group, a carbinol group, a phenol group, a mercapto group, acarboxyl group, a methacryl group, a long-chain alkyl group, an aralkylgroup, a phenyl group, a phenoxy group, an alkyl phenoxy group, along-chain fatty acid ester group, a long-chain fatty acid amide groupand a polyether group. The modified silicone compound, because of thepresence of such an organic substituent, is improved in affinity for theaforementioned cardanol-added cellulose resin and dispersibility in thecellulose resin is improved. Consequently, a resin composition excellentin impact resistance can be obtained.

As such a modified silicone compound, a modified silicone compoundproduced in accordance with a conventional method can be used.

Examples of the organic substituent contained in the modified siliconecompound include the organic substituents represented by the followingformulas (3) to (21):

where a and b each represent an integer of 1 to 50.

In the aforementioned formulas, R₁ to R₁₀, R₁₂ to R₁₅, R₁₉ and R₂₁ eachrepresent a divalent organic group. Examples of the divalent organicgroup include alkylene groups such as a methylene group, an ethylenegroup, a propylene group and a butylene group; alkyl arylene groups suchas a phenylene group and a tolylene group; oxyalkylene groups andpolyoxyalkylene groups such as —(CH₂—CH₂—O)_(c)— (c represents aninteger from 1 to 50), and —[CH₂—CH(CH₃)—O]_(d)— (d represents aninteger from 1 to 50); and —(CH₂)_(n)—NHCO— (e represents an integerfrom 1 to 8). Of these, an alkylene group is preferable andparticularly, an ethylene group and a propylene group are preferable.

In the aforementioned formulas, R₁₁, R₁₆ to R₁₈, R₂₀ and R₂₂ eachrepresent an alkyl group having at most 20 carbon atoms. Examples of thealkyl group include a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an undecyl group, a dodecyl group,a tridecyl group, a tetradecyl group and a pentadecyl group.Furthermore, the structures of the above alkyl groups may have one ormore unsaturated bonds.

The total average content of organic substituents in a modified siliconecompound desirably falls within the range where the modified siliconecompound having an appropriate particle diameter (for example, 0.1 μm ormore and 100 μm or less) can be dispersed in a matrix, i.e., acardanol-added cellulose resin, during a process for producing acellulose resin composition. If a modified silicone compound having anappropriate particle diameter is dispersed in a cardanol-added celluloseresin, stress concentration on the periphery of a silicone region havinga low elastic modulus effectively occurs. As a result, a resin moldedproduct having excellent impact resistance can be obtained. The totalaverage content of such organic substituents is preferably 0.01% by massor more and more preferably 0.1% by mass or more, and also preferably70% by mass or less and more preferably 50% by mass or less. If anorganic substituent is contained appropriately, the modified siliconecompound can be improved in affinity for a cellulose resin, the modifiedsilicone compound having an appropriate particle diameter can bedispersed in a cardanol-added cellulose resin, and further bleed out dueto separation of the modified silicone compound in a molding can besuppressed. If the total average content of the organic substituents isexcessively low, it becomes difficult to disperse a modified siliconecompound having an appropriate particle diameter in a cardanol-addedcellulose resin.

If an organic substituent of the modified polydimethyl siloxane compoundis an amino group, an epoxy group, a carbinol group, a phenol group, amercapto group, a carboxyl group or a methacryl group, the averagecontent of the organic substituent in the modified polydimethyl siloxanecompound can be obtained by the following Expression (I).

Organic substituent average content (%)=(organic substituentformula-weight/organic substituent equivalent)×100  (I)

In the Expression (I), the organic substituent equivalent is an averagemass of a modified silicone compound per organic substituent (1 mole).

When the organic substituent of the modified polydimethyl siloxanecompound is a phenoxy group, an alkylphenoxy group, a long-chain alkylgroup, an aralkyl group, a long-chain fatty acid ester group or along-chain fatty acid amide group, the average content of the organicsubstituent of the modified polydimethyl siloxane compound can beobtained from the following Expression (II).

Organic substituent average content(%)=x×w/[(1−x)×74+x×(59+w)]×100  (II)

In the Expression (II), x is an average molar fraction of the organicsubstituent-containing a siloxane repeat unit relative to all siloxanerepeat units of the modified polydimethyl siloxane compound; and w isthe formula weight of the organic substituent.

In the case where the organic substituent of the modified polydimethylsiloxane compound is a phenyl group, the average content of the phenylgroup in the modified polydimethyl siloxane compound can be obtained bythe following Expression (III).

Phenyl group average content (%)=154×x/[74×(1−x)+198×x]×100  (III)

In the Expression (III), x is an average molar fraction of the phenylgroup-containing siloxane repeat unit relative to all siloxane repeatunits in the modified polydimethyl siloxane compound (A).

In the case where the organic substituent of the modified polydimethylsiloxane compound is a polyether group, the average content of thepolyether group in the modified polydimethyl siloxane compound can beobtained by the following Expression (IV).

Polyether group average content (%)=HLB value/20×100  (IV)

In the Expression (IV), the HLB value represents the degree of affinityof a surfactant for water and oil, and is defined by the followingExpression (V) based on the Griffin Act.

HLB value=20×(sum of formula weights of hydrophilic moieties/molecularweight)  (V).

To the cellulose resin of the exemplary embodiment, two or more modifiedsilicone compounds having different affinities to the resin may beadded. In this case, dispersibility of a relative low-affinity modifiedsilicone compound (A1) is improved by a relative high-affinity modifiedsilicone compound (A2) to obtain a cellulose resin composition havingeven more excellent impact resistance. The total average content of anorganic substituent of the relatively low-affinity modified siliconecompound (A1) is preferably 0.01% by mass or more and more preferably0.1% by mass or more and also preferably 15% by mass or less and morepreferably 10% by mass or less. The total average content of an organicsubstituent of the relatively high-affinity modified silicone compound(A2) is preferably 15% by mass or more and more preferably 20% by massor more and also preferably 90% by mass or less.

The blending ratio (mass ratio) of the modified silicone compound (A1)to the modified silicone compound (A2) can be set to fall within therange of 10/90 to 90/10.

In a modified silicone compound, dimethyl siloxane repeat units andorganic substituent-containing siloxane repeat units each of which maybe homologously and continuously connected, alternately connected orconnected at random. A modified silicone compound may have a branchedstructure.

The number average molecular weight of a modified silicone compound ispreferably 900 or more and more preferably 1000 or more, and alsopreferably 1000000 or less, more preferably 300000 or less and furtherpreferably 100000 or less. If the molecular weight of a modifiedsilicone compound is sufficiently large, loss by vaporization can besuppressed in kneading with a melted cellulose resin during a processfor producing a cardanol-added cellulose resin compound. Furthermore, ifthe molecular weight of a modified silicone compound is appropriate (notexcessively large), a uniform molding having good dispersibility can beobtained.

As the number average molecular weight, a value (calibrated by apolystyrene standard sample) obtained by measuring a 0.1% chloroformsolution of a sample by GPC can be employed.

The addition amount of such a modified silicone compound is preferably,in view of obtaining sufficient addition effect, 1% by mass or morerelative to the total cellulose resin composition and more preferably 2%by mass or more. In view of sufficiently ensuring properties of acellulose resin such as strength and suppressing bleed out, the additionamount of a modified silicone compound is preferably 20% by mass or lessand more preferably 10% by mass or less.

By adding such a modified silicone compound to a cellulose resin, themodified silicone compound having an appropriate particle diameter (forexample, 0.1 to 100 μm) can be dispersed in the resin and the impactresistance of a resin composition can be improved.

As the impact resistance improver, a cardanol polymer containingcardanol as a main component may be used. Such a impact resistanceimprover has excellent compatibility with the cellulose resin of theexemplary embodiment and therefore a higher impact resistance improvingeffect can be obtained. Specific examples thereof include a cardanolpolymer obtained by adding formaldehyde to cardanol and reacting thismixture with an unsaturated bond in the straight-chain hydrocarbon ofcardanol; and a cardanol polymer obtained by adding a catalyst such assulfuric acid, phosphoric acid or diethoxytrifluoroboron and reactingunsaturated bonds of the straight-chain hydrocarbon of cardanol witheach other.

To the cellulose resin of the exemplary embodiment, if necessary,additives such as a colorant, an antioxidant and a heat stabilizer maybe added as long as they are applied to conventional resin compositions.

To the cellulose resin of the exemplary embodiment, if necessary, ageneral thermoplastic resin may be added.

Particularly, by adding a thermoplastic resin having excellentflexibility such as a thermoplastic polyurethane elastomer (TPU), impactresistance can be improved. The addition amount of such a thermoplasticresin (particularly, TPU) is, in view of obtaining sufficient additioneffect, preferably 1% by mass or more and more preferably 5% by mass ormore relative to the total composition containing the cellulose resin ofthe exemplary embodiment. In view of ensuring the properties of acellulose resin such as strength and suppressing bleed out, the additionamount of thermoplastic resin is preferably 20% by mass or less and morepreferably 15% by mass or more.

The thermoplastic polyurethane elastomer (TPU) suitable for improvingimpact resistance that can be used includes a polyurethane elastomerprepared by from a polyol, a diisocyanate and a chain extender.

Examples of the polyol include polyester polyol, polyester ether polyol,polycarbonate polyol and polyether polyol.

Examples of the polyester polyol include a polyester polyol obtained bya dehydration condensation reaction between a polyvalent carboxylic acidsuch as an aliphatic dicarboxylic acid (succinic acid, adipic acid,sebacic acid, azelaic acid, etc.), an aromatic dicarboxylic acid(phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.), an alicyclic dicarboxylic acid(hexahydrophthalic acid, hexahydroterephthalic acid,hexahydroisophthalic acid, etc.), or an acid ester or an acid anhydrideof each of these, and a polyol such as ethylene glycol, 1,3-propyleneglycol, 1,2-propylene glycol, 1,3-butane diol, 1,4-butane diol,1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, neopentylglycol, 1,3-octane diol, 1,9-nonane diol, or a mixture of these; and apolylactone diol obtained by ring-opening polymerization of a lactonemonomer such as ε-caprolactone.

Examples of the polyester ether polyol include a compound obtained by adehydration condensation reaction between a polyvalent carboxylic acidsuch as an aliphatic dicarboxylic acid (succinic acid, adipic acid,sebacic acid, azelaic acid, etc.), an aromatic dicarboxylic acid(phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.), an alicyclic dicarboxylic acid(hexahydrophthalic acid, hexahydroterephthalic acid,hexahydroisophthalic acid, etc.), or an acid ester or an acid anhydrideof each of these, and a glycol such as diethylene glycol or an alkyleneoxide adduct (propylene oxide adduct etc.) or a mixture of these.

Examples of the polycarbonate polyol include a polycarbonate polyolobtained by reacting one or two or more polyols such as ethylene glycol,1,3-propylene glycol, 1,2-propylene glycol, 1,3-butane diol, 1,4-butanediol, 1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol,neopentyl glycol, 1,8-octane diol, 1,9-nonane diol and diethylene glycolwith diethylene carbonate, dimethyl carbonate, diethyl carbonate, etc.;and further may include a copolymer of a polycaprolactone polyol (PCL)and a polyhexamethylene carbonate (PHL).

Examples of the polyether polyol include a polyethylene glycol,polypropylene glycol and polytetramethylene ether glycol, each of whichis obtained by polymerizing respective cyclic ethers: ethylene oxide,propylene oxide and tetrahydrofuran; and copolyethers of these.

Examples of the diisocyanate to be used in formation of TPU includetolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI),1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate,1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI),xylylene diisocyanate (XDI), hydrogenated XDI, triisocyanate,tetramethyl xylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate,1,8-diisocyanatemethyl octane, lysine ester triisocyanate,1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate anddicyclohexyl methane diisocyanate (hydrogenated MDI; HMDI). Of these,4,4′-diphenylmethane diisocyanate (MDI) and 1,6-hexamethylenediisocyanate (HDI) are preferably used.

Examples of the chain extender to be used in formation of TPU, alow-molecular weight polyol can be used. Examples of the low-molecularweight polyol include aliphatic polyols such as ethylene glycol,1,3-propylene glycol, 1,2-propylene glycol, 1,3-butane diol, 1,4-butanediol, 1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol,neopentyl glycol, 1,8-octane diol, 1,9-nonane diol, diethylene glycoland 1,4-cyclohexane dimethanol and glycerin; and aromatic glycols suchas 1,4-dimethylolbenzene, bisphenol A and ethylene oxide or a propyleneoxide adduct of bisphenol A.

When a silicone compound is copolymerized with a thermoplasticpolyurethane elastomer (TPU) obtained from these materials, furtherexcellent impact resistance can be obtained.

These thermoplastic polyurethane elastomers (TPU) may be used singly orin combination.

A method for producing a resin composition containing the celluloseresin of the exemplary embodiment, additives and a thermoplastic resin,is not particularly limited. For example, the resin composition can beproduced by melting and mixing additives and the cellulose resinmanually by handmixing or by use of a known mixer such as a tumblermixer, a ribbon blender, a single-axial or a multiaxial mixing extruder,and a compounding apparatus such as a kneader and kneading roll and, ifnecessary, granulating the mixture into an appropriate shape. In anotherpreferable process, additives dispersed in solvent such as an organicsolvent and a resin are mixed and furthermore, if necessary, acoagulation solvent is added to obtain a mixed composition of theadditives and the resin and thereafter, the solvent is evaporated.

The cellulose resin according to the exemplary embodiments mentionedabove can be used as a base resin for a molding material. The moldingmaterial using the cellulose resin as a base resin is suitable forforming a molded article such as housing, e.g., packaging for anelectronic device.

The base resin herein refers to a main component of the molding materialand means that other components may be contained as long as thecomponents do not prevent the function of the main component. Thecontent rate of the main component is not particularly limited; however,the content rate of the main component in a composition is 50% by massor more, preferably 70% by mass or more, more preferably 80% by mass ormore and particularly preferably 90% by mass or more.

EXAMPLES

The present invention will be more specifically described by way ofexamples below.

Synthesis Example 1 Preparation of Hydrogenated Cardanol(3-pentadecylcyclohexanol)

In a batch-system autoclave of 1.0 liter in internal volume, cardanol(20 g) obtained by distillation purification of cashew nut oil treatedwith heat, 2 g of ruthenium/carbon catalyst (Ru: 5% by mass) andtetrahydrofuran (20 mL) were placed and hydrogen was pushed in at 20kgf/cm² (1.96×10⁶ Pa) under room temperature and stirred at 80° C. for 3hours to perform a hydrogenation reaction. Thereafter, the solution wastaken out from the autoclave and filtered by use of a membrane filtermade of Teflon (registered trade mark) and having an average pore sizeof 0.2 μm to remove the ruthenium/carbon catalyst. The obtained filtratewas treated under reduced pressure while heating to distill awaytetrahydrofuran. As a result, hydrogenated cardanol (20.6 g) wasobtained as a white solid substance at room temperature.

The purity of the obtained hydrogenated cardanol was measured by liquidchromatography (product name: LC-10ADVP manufactured by ShimadzuCorporation). The purity was 99% by mass.

Furthermore, the resultant hydrogenated cardanol was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker). Thehydrogenation rate (conversion rates of a double bond in the hydrocarbonmoiety and a double bond of the aromatic ring) was 99 mol % or more.

Synthesis Example 2 Synthesis of Diisocyanate-Added Cardanol Derivative1

The temperature of hexamethylene diisocyanate (HDI) (84.5 g (0.50 mol))was raised to 50° C. while stirring. To this, hydrogenated cardanol(15.5 g (0.05 mol)) prepared in Synthesis Example 1 was added andcontinuously stirred at 80° C. for 3 hours. After the reaction solutionwas cooled to room temperature, acetonitrile (300 mL) was added. Thereaction solution was allowed to stand still in a refrigeratorovernight. Thereafter, a precipitated solid substance was separated byfiltration and dried under vacuum to obtain a diisocyanate-addedcardanol derivative in which HDI and hydrogenated cardanol were bound ina ratio of 1:1, as a white powder (18.2 g (0.04 mol)).

The obtained sample (diisocyanate-added cardanol derivative) wasmeasured by liquid chromatography (product name: LC-10ADVP manufacturedby Shimadzu Corporation). The purity was 92% by mass.

Furthermore, the solvent was distilled away from the filtrate by anevaporator to recover remaining HDI.

Synthesis Example 3 Synthesis of Diisocyanate-Added Cardanol Derivative2

The temperature of tolylene diisocyanate (TDI) (28.2 g (0.16 mol)) wasraised to 50° C. while stirring. To this, hydrogenated cardanol (25.0 g(0.08 mol)) prepared in Synthesis Example 1 was added and continuouslystirred at 80° C. for one hour. After the reaction solution was cooledto room temperature, hexane (300 mL) was added. The reaction solutionwas allowed to stand still in a refrigerator overnight. Thereafter, aprecipitated solid substance was separated by filtration and dried undervacuum to obtain diisocyanate-added cardanol derivative 2 in which TDIand hydrogenated cardanol were bound in a ratio of 1:1, as a whitepowder (20.6 g (0.04 mol)).

The obtained sample (diisocyanate-added cardanol derivative 1) wasmeasured by liquid chromatography (product name: LC-10ADVP manufacturedby Shimadzu Corporation). The purity was 98% by mass.

Furthermore, the solvent was distilled away from the filtrate by anevaporator to recover remaining TDI.

Synthesis Example 4 Synthesis of Chloridized and Monochloro Acetic AcidModified Cardanol (Chloridized and Hydrogenated Cardanol) (Correspondingto Reference Synthesis Example 2 Described Later)

Hydrogenated cardanol (m-n-pentadecylphenol manufactured by ACROSOrganics) in which an unsaturated bond of the straight-chain hydrocarbonmoiety of cardanol is hydrogenated was used as a raw material. Thephenolic hydroxy group of the hydrogenated cardanol was allowed to reactwith monochloro acetic acid for giving a carboxyl group to obtaincarboxylated and hydrogenated cardanol. Subsequently, the carboxyl groupwas chloridized with oxalyl chloride to convert into an acid chloridegroup to obtain chloridized and hydrogenated cardanol. Morespecifically, chloridized and hydrogenated cardanol was prepared inaccordance with the following procedure.

First, hydrogenated cardanol (80 g (0.26 mol)) was dissolved in methanol(120 mL). To this, an aqueous solution of sodium hydroxide (64 g (1.6mol)) dissolved in distilled water (40 mL) was added. Thereafter, asolution of monochloro acetic acid (66 g (0.70 mol)) manufactured byKanto Chemical Co., Inc. dissolved in methanol (50 mL) was addeddropwise at room temperature. After completion of dropwise addition,stirring was continued while refluxing at 73° C. for 4 hours. After thereaction solution was cooled to room temperature, the reaction mixturewas acidified with a diluted hydrochloric acid until pH became 1. Tothis, methanol (250 mL) and diethyl ether (500 mL) and further distilledwater (200 mL) were added. The resultant water layer was separated by aseparating funnel and discarded. The resultant ether layer was washedtwice with distilled water (400 mL). To the ether layer, magnesiumanhydride was added to dry the ether layer, which was then separated byfiltration. The filtrate (ether layer) was concentrated by an evaporator(90° C./3 mmHg) under reduced pressure to obtain a yellow brown powderycrude product as the residue. The crude product was recrystallized fromn-hexane and dried under vacuum to obtain a white powder of carboxylatedand hydrogenated cardanol (46 g (0.12 mol)).

The carboxylated and hydrogenated cardanol (46 g (0.12 mol)) thusobtained was dissolved in dehydrated chloroform (250 mL), and oxalylchloride (24 g (0.19 mol)) and N,N-dimethylformamide (0.25 mL (3.2mmol)) were added. The mixture was stirred for 72 hours at roomtemperature. Chloroform, excessive oxalyl chloride andN,N-dimethylformamide were distillated away under reduced pressure toobtain chloridized and hydrogenated cardanol (48 g (0.13 mol)).

Example 1

Diisocyanate-added cardanol derivative 1 prepared in Synthesis Example 2was allowed to bind to cellulose acetate (trade name: L-70 manufacturedby Daicel Chemical Industries, Ltd., the number of acetic acid groupsadded to a single glucose unit of cellulose (degree of substitution byacetylation: DS_(Ace))=2.4) to obtain grafted cellulose acetate. Morespecifically, grafted cellulose acetate was prepared in accordance withthe following procedure.

Cellulose acetate (10.0 g (the amount of hydroxy group: 0.023 mol)) wasdissolved in dehydrated dioxane (200 mL), and dibutyl tin dilaurate (0.1g) was added as a reaction catalyst. To the solution, a dioxane solution(100 mL) dissolving diisocyanate-added cardanol derivative 1 (13.7 g(0.029 mol)) prepared in Synthesis Example 2 was added and heated toreflux at 80° C. for 10 hours. The reaction solution was cooled to roomtemperature, and a precipitate was removed by filtration (suctionfiltration). The efficiency of the filtration at this time was evaluatedin accordance with the following criteria. The results are shown inTable 4. In the filtration, a filter paper manufactured by KiriyamaGlass Co. (product name: Kiriyama filter, Form: No. 5B, retentionparticle size: 4 μm, diameter: 150 mm, thickness: 0.22 mm) was used.

(Evaluation Criteria)

⊚: good (clogging of filter does not occur), ◯: filterable (clogging offilter slightly occurs but filtration can be made), x: non-filterable.

The filtrate was slowly added dropwise to methanol (3 L) while stirringto allow reprecipitation, and a solid substance was separated byfiltration. The solid substance separated by filtration was driedovernight in the air and further dried under vacuum at 105° C. for 5hours to obtain grafted cellulose acetate (15.7 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.57.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 2→Example 1) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the followingprocedure. The results are shown in Table 1.

[Evaluation of Thermoplasticity (Press Moldability)]

Press molding was performed in the following conditions to obtain amolded product. At that time, moldability was evaluated in accordancewith the following criteria.

(Molding Conditions)

Temperature: 200° C., Time: 2 minutes, Pressure: 100 kgf (9.8×10² N),

Size of molded product: Thickness: 2 mm, Width: 13 mm, Length: 80 mm

(Evaluation Criteria)

◯: Good, Δ: not good (void, sink mark or partial uncharged portion wasobserved), x: cannot be molded.

[Measurement of Glass Transition Temperature (Heat ResistanceEvaluation)]

Glass transition temperature was measured by DSC (product name: DSC6200,manufactured by Seiko Instruments Inc.).

[Bending Test]

The molded product obtained by the aforementioned molding process wassubjected to a bending test in accordance with JIS K7171.

[Measurement of Water Absorption Rate]

Water absorption rate was measured in accordance with JIS K7209.

[Lightness of Color]

The molded product obtained by the aforementioned molding process wassubjected to measurement of lightness L* (L*a*b* system: L*=0 to 100),which indicates whiteness of a color, by use of a spectrocolorimeter(JX777 (trade name) manufactured by Color Techno System Corporation,light source: D65/2°).

[Determination of Plant-Component Ratio]

A cellulose component and a cardanol component were regarded as plantcomponents. The total content rate (% by mass) of the plant componentsrelative to the whole sample was obtained. Assuming that the cellulosecomponent herein corresponds to that having a structure represented byFormula (1) above in which a hydroxy group is not acylated or grafted,and that the cardanol component corresponds to that having a structurerepresented by Formula (2) above, calculation was made.

Example 2

Diisocyanate-added cardanol derivative 2 prepared in Synthesis Example 3was allowed to bind to cellulose acetate (trade name: L-70, manufacturedby Daicel Chemical Industries, Ltd., the number of acetic acid groupsadded to a single glucose unit of cellulose (degree of substitution byacetylation: DS_(Ace))=2.4) to obtain grafted cellulose acetate. Morespecifically, the grafted cellulose acetate was prepared in accordancewith the following procedure.

Cellulose acetate (10.0 g (hydroxy-group amount: 0.023 mol)) wasdissolved in dehydrated dioxane (200 mL), and dibutyl tin dilaurate (0.1g) was added as a reaction catalyst. To the solution, a dioxane solution(100 mL) dissolving diisocyanate-added cardanol derivative 2 (29.8 g(0.062 mol)) prepared in Synthesis Example 3 was added. The reactionsolution was heated to reflux at 80° C. for 10 hours. The reactionsolution was slowly added dropwise to methanol (3 L) while stirring toallow reprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate (15.6 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.55.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 3→Example 2) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same manneras in Example 1. The results are shown in Table 1.

Example 3

Diisocyanate-added cardanol derivative 1 prepared in Synthesis Example 2was allowed to bind to cellulose acetate (the acetylation amount wascontrolled by a predetermined method, the number of acetic acidmolecules added to a single glucose unit of cellulose (degree ofsubstitution by acetylation: DS_(Ace))=2.65) to obtain grafted celluloseacetate. More specifically, the grafted cellulose acetate was preparedin accordance with the following procedure.

Cellulose acetate (10.0 g (hydroxy-group amount: 0.013 mol)) wasdissolved in dehydrated dioxane (200 mL), and dibutyl tin dilaurate (0.1g) was added as a reaction catalyst. To the solution, a dioxane solution(100 mL) dissolving diisocyanate-added cardanol derivative 1 (9.1 g(0.019 mol)) prepared in Synthesis Example 2 was added. The reactionsolution was heated to reflux at 80° C. for 10 hours. The reactionsolution was cooled to room temperature and a precipitate was removed byfiltration. The filtrate was slowly added dropwise to methanol (3 L)while stirring to allow reprecipitation. The resultant solid substancewas separated by filtration, dried overnight in the air and furtherdried under vacuum at 105° C. for 5 hours to obtain grafted celluloseacetate (13.5 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.33.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 2→Example 3) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 2.

Example 4

Diisocyanate-added cardanol derivative 2 prepared in Synthesis Example 3was allowed to bind to cellulose acetate (the acetylation amount wascontrolled by a predetermined method, the number of acetic acidmolecules added to a single glucose unit of cellulose (degree ofsubstitution by acetylation: DS_(Ace))=2.65) to obtain grafted celluloseacetate. More specifically, the grafted cellulose acetate was preparedin accordance with the following procedure.

Cellulose acetate (10.0 g (hydroxy-group amount: 0.013 mol)) wasdissolved in dehydrated dioxane (200 mL), and dibutyl tin dilaurate (0.1g) was added as a reaction catalyst. To the solution, a dioxane solution(100 mL) dissolving diisocyanate-added cardanol derivative 2 (19.9 g(0.041 mol)) prepared in Synthesis Example 3 was added. The reactionsolution was heated to reflux at 80° C. for 10 hours. The reactionsolution was slowly added dropwise to methanol (3 L) while stirring toallow reprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate (13.6 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.32.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 3→Example 4) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 2.

Example 5

Diisocyanate-added cardanol derivative 1 prepared in Synthesis Example 2was allowed to bind to cellulose acetate propionate (trade name:CAP-482-20, manufactured by Eastman Chemical Company, the number ofacetic acid molecules added to a single glucose unit of cellulose(degree of substitution by acetylation: DS_(Ace))=0.18; the number ofpropionic acid molecules added to a single glucose unit of cellulose(degree of substitution by propionation: DS_(Pr))=2.49) to obtaingrafted cellulose acetate propionate. More specifically, the graftedcellulose acetate propionate was prepared in accordance with thefollowing procedure.

Cellulose acetate propionate (10.0 g (hydroxy-group amount: 0.013 mol))was dissolved in dehydrated dioxane (200 mL), and dibutyl tin dilaurate(0.1 g) was added as a reaction catalyst. To the solution, a dioxanesolution (100 mL) dissolving diisocyanate-added cardanol derivative 1(7.7 g (0.016 mol)) prepared in Synthesis Example 2 was added. Thereaction solution was heated to reflux at 80° C. for 6 hours. Thereaction solution was cooled to room temperature and a precipitate wasremoved by filtration. The filtrate was slowly added dropwise tomethanol (3 L) while stirring to allow reprecipitation. The resultantsolid substance was separated by filtration, dried overnight in the airand further dried under vacuum at 105° C. for 5 hours to obtain graftedcellulose acetate propionate (12.5 g).

The obtained sample (grafted cellulose acetate propionate) was measuredby ¹H-NMR (product name: AV-400, 400 MHz, manufactured by Bruker), andDS_(CD) was 0.23.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 2→Example 5) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 3.

Example 6

Diisocyanate-added cardanol derivative 2 prepared in Synthesis Example 3was allowed to bind to cellulose acetate propionate (trade name:CAP-482-20, manufactured by Eastman Chemical Company, the number ofacetic acid molecules added to a single glucose unit of cellulose(degree of substitution by acetylation: DS_(Ace))=0.18; the number ofpropionic acid molecules added to a single glucose unit of cellulose(degree of substitution by propionation: DS_(Pr))=2.49) to obtaingrafted cellulose acetate propionate. More specifically, the graftedcellulose acetate propionate was prepared in accordance with thefollowing procedure.

Cellulose acetate propionate (10.0 g (hydroxy-group amount: 0.013 mol))was dissolved in dehydrated dioxane (200 mL), and dibutyl tin dilaurate(0.1 g) was added as a reaction catalyst. To the solution, a dioxanesolution (100 mL) dissolving diisocyanate-added cardanol derivative 2(17.2 g (0.033 mol)) prepared in Synthesis Example 3 was added. Thereaction solution was heated to reflux at 80° C. for 6 hours. Thereaction solution was slowly added dropwise to methanol (3 L) whilestirring to allow reprecipitation. The resultant solid substance wasseparated by filtration, dried overnight in the air and further driedunder vacuum at 105° C. for 5 hours to obtain grafted cellulose acetatepropionate (12.6 g).

The obtained sample (grafted cellulose acetate propionate) was measuredby ¹H-NMR (product name: AV-400, 400 MHz, manufactured by Bruker), andDS_(CD) was 0.22.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 3→Example 6) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 3.

Example 7

Diisocyanate-added cardanol derivative 1 prepared in Synthesis Example 2was allowed to bind to cellulose acetate (trade name: L-70 manufacturedby Daicel Chemical Industries, Ltd., the number of acetic acid moleculesadded to a single glucose unit of cellulose (degree of substitution byacetylation: DS_(Ace))=2.4) to obtain grafted cellulose acetate. Morespecifically, grafted cellulose acetate was prepared in accordance withthe following procedure.

Cellulose acetate (10.0 g (the amount of hydroxy group: 0.023 mol)) wasdissolved in methyl ethyl ketone (200 mL), and dibutyl tin dilaurate(0.1 g) was added as a reaction catalyst. To the solution, a methylethyl ketone solution (100 mL) dissolving diisocyanate-added cardanolderivative 1 (13.7 g (0.029 mol)) prepared in Synthesis Example 2 wasadded and heated to reflux at 80° C. for 10 hours. To the reactionsolution, a phosphoric acid powder (0.15 g) was added as a catalystinactivator. After the reaction solution was heated to reflux at 80° C.for 30 minutes, the solution was cooled to room temperature and aprecipitate was removed by filtration. The efficiency of the filtrationat this time was evaluated in accordance with the same criteria as inExample 1. The results are shown in Table 4.

The solvent was removed from the filtrate under reduced pressure torecover a solid substance. The resultant solid substance was dried undervacuum at 105° C. for 5 hours to obtain grafted cellulose acetate (15.7g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.57.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 2→Example 7) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 1.

Example 8

Diisocyanate-added cardanol derivative 2 prepared in Synthesis Example 3was allowed to bind to cellulose acetate (trade name: L-70, manufacturedby Daicel Chemical Industries, Ltd., the number of acetic acid moleculesadded to a single glucose unit of cellulose (degree of substitution byacetylation: DS_(Ace))=2.4) to obtain grafted cellulose acetate. Morespecifically, the grafted cellulose acetate was prepared in accordancewith the following procedure.

Cellulose acetate (10.0 g (hydroxy-group amount: 0.023 mol)) wasdissolved in methyl ethyl ketone (200 mL), and dibutyl tin dilaurate(0.1 g) was added as a reaction catalyst. To the solution, a methylethyl ketone solution (100 mL) dissolving diisocyanate-added cardanolderivative 2 (29.8 g (0.062 mol)) prepared in Synthesis Example 3 wasadded. The reaction solution was heated to reflux at 80° C. for 10hours. To the reaction solution, a phosphoric acid powder (0.15 g) wasadded as a catalyst inactivator. After the reaction solution was heatedto reflux at 80° C. for 30 minutes, the solvent was removed underreduced pressure to recover a solid substance. The resultant solidsubstance was dried under vacuum at 105° C. for 5 hours to obtaingrafted cellulose acetate (15.6 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.55.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 3→Example 8) is shown inFIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 1.

Examples 9 to 15

Diisocyanate-added cardanol derivative 1 prepared in Synthesis Example 2was allowed to bind to cellulose acetate (trade name: L-70 manufacturedby Daicel Chemical Industries, Ltd., the number of acetic acid moleculesadded to a single glucose unit of cellulose (degree of substitution byacetylation: DS_(Ace))=2.4) to obtain grafted cellulose acetate. Morespecifically, grafted cellulose acetate was prepared by use of each ofthe solvents shown in Table 4 in accordance with the followingprocedure.

Cellulose acetate (10.0 g (the amount of hydroxy group: 0.023 mol)) wasdissolved in each of the solvents (200 mL) shown in Table 4, and dibutyltin dilaurate (0.1 g) was added as a reaction catalyst. To the solution,the same type of solution (100 mL) dissolving diisocyanate-addedcardanol derivative 1 (13.7 g (0.029 mol)) prepared in Synthesis Example2 was added and heated to reflux at 80° C. for 10 hours. To the reactionsolution, a phosphoric acid powder (0.15 g) was added as a catalystinactivator. After the reaction solution was heated to reflux at 80° C.for 30 minutes, the solution was cooled to room temperature and aprecipitate was removed by filtration. The efficiency of the filtrationat this time was evaluated in accordance with the same criteria as inExample 1. The results are shown in Table 4.

The solvent was removed from the filtrate under reduced pressure torecover a solid substance. The resultant solid substance was dried undervacuum at 105° C. for 5 hours to obtain grafted cellulose acetate.

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and the resultsof DS_(CD) are shown in Table 4.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 1→Synthesis Example 2→Examples 9 to 15) isshown in FIG. 1.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 5.

Reference Example 101

Chloridized and monochloro acetic acid modified cardanol (chloridizedand hydrogenated cardanol) prepared in Synthesis Example 3 (ReferenceSynthesis Example 2) was allowed to bind to cellulose acetate (tradename: L-70 manufactured by Daicel Chemical Industries, Ltd., the numberof acetic acid molecules added to a single glucose unit of cellulose(degree of substitution by acetylation: DS_(Ace))=2.4) to obtain graftedcellulose acetate. More specifically, grafted cellulose acetate wasprepared in accordance with the following procedure.

Cellulose acetate (15.8 g (the amount of hydroxy group: 0.036 mol)) wasdissolved in dehydrated dioxane (200 mL), and triethylamine (5.0 mL(0.036 mol)) was added as a reaction catalyst and an acid trappingagent. To the solution, a dioxane solution (100 mL) dissolvingchloridized and hydrogenated cardanol (41.2 g (0.108 mol)) prepared inSynthesis Example 3 was added and heated to reflux at 100° C. for 5hours. The reaction solution was slowly added dropwise to methanol (3 L)while stirring to allow reprecipitation. The resultant solid substancewas separated by filtration, dried overnight in the air and furtherdried under vacuum at 105° C. for 5 hours to obtain grafted celluloseacetate (19 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.50.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 4→Reference Example 101) is shown in FIG. 2.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 1.

Reference Example 102

Chloridized and monochloro acetic acid modified cardanol (chloridizedand hydrogenated cardanol) prepared in Synthesis Example 4 (ReferenceSynthesis Example 2) was allowed to bind to cellulose acetate (theacetylation amount was controlled by a predetermined method. The numberof acetic acid molecules added to a single glucose unit of cellulose(degree of substitution by acetylation: DS_(Ace))=2.65) to obtaingrafted cellulose acetate. More specifically, grafted cellulose acetatewas prepared in accordance with the following procedure.

Cellulose acetate (12 g (the amount of hydroxy group: 0.015 mol)) wasdissolved in dehydrated dioxane (200 mL), and triethylamine (2.1 mL(0.015 mol)) was added as a reaction catalyst and an acid trappingagent. To the solution, a dioxane solution (100 mL) dissolvingchloridized and hydrogenated cardanol (20.6 g (0.054 mol)) prepared inSynthesis Example 3 was added and heated to reflux at 100° C. for 5hours. The reaction solution was slowly added dropwise to methanol (3 L)while stirring to allow reprecipitation. The resultant solid substancewas separated by filtration, dried overnight in the air and furtherdried under vacuum at 105° C. for 5 hours to obtain grafted celluloseacetate (14 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.34.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 4→Reference Example 102) is shown in FIG. 2.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 2.

Reference Example 103 Corresponding to Reference Example 24 DescribedLater

Chloridized and monochloro acetic acid modified cardanol (chloridizedand hydrogenated cardanol) prepared in Synthesis Example 4 (ReferenceSynthesis Example 2) was allowed to bind to cellulose acetate propionate(trade name: CAP-482-20, manufactured by Eastman Chemical Company, thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of substitution by acetylation: DS_(Ace))=0.18; thenumber of propionic acid molecules added to a single glucose unit ofcellulose (degree of substitution by propionation: DS_(Pr))=2.49) toobtain grafted cellulose acetate propionate. More specifically, thegrafted cellulose acetate propionate was prepared in accordance with thefollowing procedure.

Cellulose acetate propionate (10 g (hydroxy-group amount: 0.010 mol))was dissolved in dehydrated dioxane (200 mL), and triethylamine (2.5 mL(0.018 mol)) was added as a reaction catalyst and an acid trappingagent. To the solution, a dioxane solution (100 mL) dissolvingchloridized and hydrogenated cardanol (13 g (0.035 mol)) prepared inReference Synthesis Example 2 was added. The reaction solution washeated to reflux at 100° C. for 5 hours. The reaction solution wasslowly added dropwise to methanol (3 L) while stirring to allowreprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate propionate (13g).

The obtained sample (grafted cellulose acetate propionate) was measuredby ¹H-NMR (product name: AV-400, 400 MHz, manufactured by Bruker), andDS_(CD) was 0.33.

The process chart from raw-material cardanol until the sample isobtained (Synthesis Example 4→Reference Example 103) is shown in FIG. 2.

Furthermore, the sample was evaluated in accordance with the same methodas in Example 1. The results are shown in Table 3.

Reference Examples 104 to 106

Using solvents (toluene, isopropanol, 1-butanol) shown in Table 4,diisocyanate-added cardanol derivative 1 of Synthesis Example 2 wastried to bind to cellulose acetate (trade name: L-70 manufactured byDaicel Chemical Industries, Ltd., the number of acetic acid moleculesadded to a single glucose unit of cellulose (degree of substitution byacetylation: DS_(Ace))=2.4). However, the solubilities of the reactantin the solvents were low and grafting was not sufficiently performed andthus, a desired grafted cellulose acetate was not obtained.

TABLE 1 Reference Example Example 1 Example 2 Example 7 Example 8 101Amount DS_(Ace) 2.4 2.4 2.4 2.4 2.4 of acetyl Mass fraction (%) 19 20 1920 24 group Amount DS_(CD) HDI TDI HDI TDI 0 of modified with 0.57 0.550.57 0.55 cardanol diisocyanate derivative DS_(CD) 0 0 0 0 0.50 modifiedwith monochloro acetic acid Mass fraction (%) 51 50 51 50 40 Additionamount of plasticizer 0 0 0 0 0 (% by mass) Bending strength (MPa) 55 6554 65 57 Bending elasticity (GPa) 1.4 1.7 1.4 1.7 1.5 Bend-breakingstrain (%) >10 >10 >10 >10 >10 Glass transition temperature 139 146 140145 142 (° C.) (heat resistance) Thermoplasticity ◯ ◯ ◯ ◯ ◯ (pressmoldability) Water absorption rate (%) 0.9 0.9 0.9 0.9 1.2 Lightness ofcolor (L*) 68.8 60.4 67.8 60.9 5.9 Plant component ratio (%) 61 61 61 6171

TABLE 2 Reference Example 3 Example 4 Example 102 Amount of DS_(Ace)2.65 2.65 2.65 acetyl Mass fraction (%) 26 26 30 group Amount of DS_(CD)0.33 0.32 0 cardanol modified with (HDI) (TDI) derivative diisocyanateDS_(CD) 0 0 0.34 modified with monochloro acetic acid-acid chloridizedMass fraction (%) 37 38 30 Addition amount of plasticizer 0 0 0 (% bymass) Bending strength [MPa] 90 98 91 Bending elasticity [GPa] 2.0 2.22.0 Bend-breaking strain [%] >10 >10 >10 Glass transition temperature [°C.] 146 149 132 (heat resistance) Thermoplasticity ◯ ◯ ◯ (pressmoldability) Water absorption rate [%] 1.0 1.0 1.4 Lightness of color[L*] 70.3 62.2 13.5 Plant component ratio [%] 60 59 67

TABLE 3 Reference Example Example 5 Example 6 103 Amount of DS_(Ace)0.18 0.18 0.18 acetyl group Mass fraction (%) 1.8 1.8 1.8 Amount ofDS_(Pr) 2.49 2.49 2.49 propionyl Mass fraction (%) 34 34 27 group Amountof DS_(CD) 0.23 0.22 0 cardanol modified with (HDI) (TDI) derivativediisocyanate DS_(CD) 0 0 0.33 modified with monochloro acetic acid-acidchloridized Mass fraction (%) 26 26 27 Addition amount of plasticizer 00 0 (% by mass) Bending strength [MPa] 64 86 49 Bending elasticity [GPa]1.7 2.4 1.4 Bend-breaking strain [%] >10 >10 >10 Glass transitiontemperature [° C.] 105 115 92 (heat resistance) Thermoplasticity ◯ ◯ ◯(press moldability) Water absorption rate [%] 0.80 0.75 0.76 Lightnessof color [L*] 69.1 61.1 16.7 Plant component ratio [%] 54 54 61

TABLE 4 Polarity Specific Filter- DS_(CD) of Type of solvent valuegravity ability product Example 1 Dioxane 0.164 1.033 ◯ 0.57 Example 9Tetrahydrofuran 0.207 0.886 ⊚ 0.54 Example 10 Ethyl acetate 0.228 0.894⊚ 0.55 Example 11 Chloroform 0.259 1.498 ◯ 0.56 Example 12 Pyridine0.302 0.982 ◯ 0.53 Example 7 Methyl ethyl ketone 0.327 0.805 ⊚ 0.57Example 13 Acetone 0.355 0.786 ⊚ 0.57 Example 14 Dimethylformamide 0.3860.944 ⊚ 0.56 Example 15 Dimethylsulfoxide 0.444 1.092 ◯ 0.55 ReferenceToluene 0.099 0.867 — — Example 104 Reference Isopropanol 0.546 0.785 —— Example 105 Reference 1-Butanol 0.654 0.81 — — Example 106

TABLE 5 Example Example Example Example Example Example Example 9 10 1112 13 14 15 Amount DS_(Ace) 2.4 2.4 2.4 2.4 2.4 2.4 2.4 of acetyl Massfraction 20 20 20 20 19 20 20 group (%) Amount DS_(CD) HDI HDI HDI HDIHDI HDI HDI of modified with 0.54 0.55 0.56 0.53 0.57 0.56 0.55 cardanoldiisocyanate derivative DS_(CD) 0 0 0 0 0 0 0 modified with monochloroacetic acid Mass fraction 50 50 51 49 51 51 50 (%) Addition amount of 00 0 0 0 0 0 plasticizer (% by mass) Bending strength (MPa) 55 56 55 5554 55 55 Bending elasticity (GPa) 1.4 1.4 1.4 1.4 1.4 1.4 1.4Bend-breaking strain (%) >10 >10 >10 >10 >10 >10 >10 Glass transitiontemperature 139 140 138 140 138 139 139 (° C.) (heat resistance)Thermoplasticity ◯ ◯ ◯ ◯ ◯ ◯ ◯ (press moldability) Water absorption rate(%) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Lightness of color (L*) 69.1 69.0 68.868.9 68.3 68.4 68.6 Plant component ratio (%) 61 61 61 61 61 61 61

As is apparent from comparison between Examples 1, 2, 7 to 15 (cardanoladded cellulose resins obtained by grafting using a diisocyanatecompound) and Reference Example 101 (cardanol added cellulose resinobtained by grafting using monochloro acetic acid), it is found that thecardanol added cellulose resins of Examples 1, 2, 7 to 15 are greatlyimproved in lightness of color while keeping satisfactory strength, heatresistance (Tg) and water resistance. Furthermore, as is apparent fromcomparison between Examples 1, 2, 7 to 15 and Reference Examples 104 to106, it is found that cardanol added cellulose resin can be easilyproduced with a high reaction rate by using a solvent having a polarityvalue of 0.15 or more and 0.5 or less.

Furthermore, as is apparent from comparison of process charts shown inFIG. 1 and FIG. 2, it is found that the cardanol added cellulose resinsaccording to Examples 1 and 2 and Examples 7 to 15 can be produced witha few manufacturing steps without by-products and thus can be easilyproduced.

Examples 3 and 4 and Reference Example 102 are examples in which thenumber of acetyl groups added to the hydroxy group of cellulose isincreased compared to Examples 1 and 2 and Reference Example 101. Evenin this case, as is apparent from comparison between Examples 3 and 4(cardanol added cellulose resins obtained by grafting using adiisocyanate compound) and Reference Example 102 (cardanol addedcellulose resin obtained by grafting using monochloro acetic acid), itis found that the cardanol added cellulose resins of Examples 3 and 4are greatly improved in lightness of color while keeping satisfactorystrength, heat resistance (Tg) and water resistance.

Furthermore, as is apparent from comparison of process charts shown inFIG. 1 and FIG. 2, it is found that the cardanol added cellulose resinsaccording to Examples 3 and 4 can be produced with a few manufacturingsteps without by-products and thus can be easily produced.

Examples 5 and 6 and Reference Example 103 are examples of a celluloseresin prepared by using a cellulose derivative in which a propionylgroup is added to a hydroxy group, in addition to an acetyl group. Evenin this case, as is apparent from comparison between Examples 5 and 6(cardanol added cellulose resins obtained by grafting using adiisocyanate compound) and Reference Example 103 (cardanol addedcellulose resin obtained by grafting using monochloro acetic acid), itis found that the cardanol added cellulose resins of Examples 5 and 6are greatly improved in lightness of color while keeping satisfactorystrength, heat resistance (Tg) and water resistance.

Furthermore, as is apparent from comparison of process charts shown inFIG. 1 and FIG. 2, it is found that the cardanol added cellulose resinsaccording to Examples 5 and 6 can be produced with a few manufacturingsteps without by-products and thus can be easily produced.

In addition, a cardanol added cellulose resin obtained by grafting usinga compound other than a diisocyanate compound will be more specificallydescribed by use of specific examples.

Reference Synthesis Example 1 Cardanol Derivative 1 (Preparation ofChloridized and Succinic Acid-Modified Cardanol)

Hydrogenated cardanol (m-n-pentadecylphenol manufactured by ACROSOrganics), in which an unsaturated bond(s) of the straight-chainhydrocarbon moiety of cardanol are hydrogenated, was used as a rawmaterial. When the hydrogenated cardanol was measured by ¹H-NMR (productname: AV-400, 400 MHz, manufactured by Bruker), no unsaturated bond wasdetected. Thus, it was confirmed that a hydrogenation rate is at least90% by mole or more. The phenolic hydroxy group of the cardanol wasreacted with succinic anhydride to add a carboxyl group to obtaincarboxylated and hydrogenated cardanol. Next, the carboxyl group wasconverted into an acid chloride group by chloridizing it with oxalylchloride to obtain chloridized and hydrogenated cardanol. Morespecifically, the chloridized and hydrogenated cardanol was prepared inaccordance with the following procedure.

First, succinic anhydride (33 g (0.33 mol)) was dissolved in dehydratedchloroform (250 mL). To this, dehydrated pyridine (5.0 mL (0.062 mol))and a raw material, i.e., hydrogenated cardanol (50 g (0.16 mol)) wereadded. The reaction solution was heated to reflux under a nitrogenatmosphere at 70° C. for 24 hours, cooled to room temperature.Thereafter, a crystal of succinic anhydride precipitated was separatedby filtration. The chloroform solution filtrated was washed twice with0.1 mol/L hydrochloric acid (250 mL) and further washed twice with water(250 mL). After washing, the chloroform solution was dehydrated withmagnesium sulfate and magnesium sulfate was separated by filtration andchloroform was distillated away under reduced pressure to obtain a brownsolid substance of carboxylated and hydrogenated cardanol (60 g (0.15mol)).

The resultant carboxylated and hydrogenated cardanol (50 g (0.12 mol))was dissolved in dehydrated chloroform (250 mL). To this, oxalylchloride (24 g (0.19 mol)) and N,N-dimethylformamide (0.25 mL (3.2mmol)) were added. The reaction solution was stirred at room temperaturefor 72 hours. Chloroform, excessive oxalyl chloride andN,N-dimethylformamide were distillated away under reduced pressure toobtain chloridized and hydrogenated cardanol (52 g (0.12 mol)).

Reference Synthesis Example 2 Cardanol Derivative 2 (Preparation ofChloridized and Monochloroacetic Acid-Modified Cardanol)

Hydrogenated cardanol (m-n-pentadecylphenol manufactured by ACROSOrganics), in which an unsaturated bond(s) of the straight-chainhydrocarbon moiety of cardanol are hydrogenated, was used as a rawmaterial. The phenolic hydroxy group of the cardanol was reacted withmonochloroacetic acid to add a carboxyl group to obtain carboxylated andhydrogenated cardanol. Next, the carboxyl group was converted into anacid chloride group by chloridizing it with oxalyl chloride to obtainchloridized and hydrogenated cardanol. More specifically, thechloridized and hydrogenated cardanol was prepared in accordance withthe following procedure.

First, hydrogenated cardanol (80 g (0.26 mol)) was dissolved in methanol(120 mL). To this, an aqueous solution of sodium hydroxide (64 g (1.6mol)) dissolved in distilled water (40 mL) was added. Thereafter, atroom temperature, a solution of monochloro acetic acid (66 g (0.70 mol))(manufactured by Kanto Chemical Co., Inc.) dissolved in methanol (50 mL)was added dropwise. After completion of the dropwise addition, thereaction solution was continuously stirred while refluxing at 73° C. for4 hours. The reaction solution was cooled to room temperature and thereaction mixture was acidified with a diluted hydrochloric acid until pHbecame 1. To this, methanol (250 mL) and diethyl ether (500 mL) andfurther distilled water (200 mL) were added. The resultant water layerwas separated by a separating funnel and discarded. The ether layer waswashed twice with distilled water (400 mL). To the ether layer,magnesium anhydride was added to dry the ether layer and then separatedby filtration. The filtrate (ether layer) was concentrated by anevaporator (90° C./3 mmHg) under reduced pressure to obtain a yellowbrown powdery crude product as the residue. The crude product wasrecrystallized from n-hexane and dried under vacuum to obtain whitepowder of carboxylated and hydrogenated cardanol (46 g (0.12 mol)).

The resultant carboxylated and hydrogenated cardanol (46 g (0.12 mol))was dissolved in dehydrated chloroform (250 mL). To this, oxalylchloride (24 g (0.19 mol)) and N,N-dimethylformamide (0.25 mL (3.2 mmol)were added. The mixture was stirred at room temperature for 72 hours.Chloroform, excessive oxalyl chloride and N,N-dimethylformamide weredistillated away under reduced pressure to obtain chloridized andhydrogenated cardanol (48 g (0.13 mol)).

Reference Synthesis Example 3 Preparation of Biphenylacetyl Chloride

Biphenylacetic acid (6.0 g (0.028 mol)) manufactured by Sigma-AldrichCo. LLC was dissolved in dehydrated chloroform (60 ml). To this, oxalylchloride (3.7 g (0.029 mol)) and N,N-dimethylformamide (0.04 ml (0.51mmol)) were added. The mixture was stirred at room temperature for 72hours. Chloroform, excessive oxalyl chloride and N,N-dimethylformamidewere distillated away under reduced pressure to obtain biphenylacetylchloride (6.5 g (0.028 mol)).

Reference Example 1

The chloridized and hydrogenated cardanol (cardanol derivative 1)prepared in Reference Synthesis Example 1 was allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, the graftedcellulose acetate was prepared in accordance with the followingprocedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (46 g (0.11 mol)) prepared in Reference SynthesisExample 1 was added. The reaction solution was heated to reflux at 100°C. for 6 hours. The reaction solution was slowly added dropwise tomethanol (3 L) while stirring to allow reprecipitation. The resultantsolid substance was separated by filtration, dried overnight in the airand further dried under vacuum at 105° C. for 5 hours to obtain graftedcellulose acetate (20 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.90.

Furthermore, the sample was evaluated in the following procedure. Theresults are shown in Table 101A.

[Evaluation of Thermoplasticity (Press Moldability)]

Press molding was performed in the following conditions to obtain amolded product. At that time, moldability was evaluated in accordancewith the following criteria.

(Molding Conditions)

Temperature: 170° C., Time: 2 minutes, Pressure: 100 kgf (9.8×10² N),

Size of molded product: Thickness: 2 mm, Width: 13 mm, Length: 80 mm

(Evaluation Criteria)

◯: Good, Δ: not good (void, sink mark or partial uncharged portion wasobserved), x: cannot be molded.

[Measurement of Glass Transition Temperature (Heat ResistanceEvaluation)]

Glass transition temperature was measured by DSC (product name: DSC6200,manufactured by Seiko Instruments Inc.).

[Bending Test]

The molded product obtained by the aforementioned molding process wassubjected to a bending test in accordance with JIS K7171.

[Tensile Test]

A solution of a sample (2 g) dissolved in chloroform (20 mL) wasprepared. The solution was subjected to casting and a film of 10 mm inwidth, 60 mm in length and 0.2 mm in thickness was prepared by cuttingout by a cutter knife. The film was subjected to a tensile test inaccordance with JIS K7127.

[Measurement of Water Absorption Rate]

Water absorption rate was obtained by measurement in accordance with JISK7209.

[Determination of Plant-Component Ratio]

A cellulose component and a cardanol component were regarded as plantcomponents. The total content rate (% by mass) of the plant componentsrelative to the whole sample was obtained. Assuming that the cellulosecomponent herein corresponds to that having a structure represented byFormula (1) above in which a hydroxy group is not acylated or grafted,and that the cardanol component corresponds to that having a structurerepresented by Formula (2) above, calculation was made.

Reference Example 2

The chloridized and hydrogenated cardanol (cardanol derivative 1)prepared in Reference Synthesis Example 1 was allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, the graftedcellulose acetate was prepared in accordance with the followingprocedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (23 g (0.054 mol)) prepared in Reference SynthesisExample 1 was added. The reaction solution was heated to reflux at 100°C. for 6 hours. The reaction solution was slowly added dropwise tomethanol (3 L) while stirring to allow reprecipitation. The resultantsolid substance was separated by filtration, dried overnight in the airand further dried under vacuum at 105° C. for 5 hours to obtain graftedcellulose acetate (16 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.55.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101A.

Reference Example 3

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, the graftedcellulose acetate was prepared in accordance with the followingprocedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (14 g (0.037 mol)) prepared in Reference SynthesisExample 2 was added. The reaction solution was heated to reflux at 100°C. for 3 hours. The reaction solution was slowly added dropwise tomethanol (3 L) while stirring to allow reprecipitation. The resultantsolid substance was separated by filtration, dried overnight in the airand further dried under vacuum at 105° C. for 5 hours to obtain graftedcellulose acetate (15 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.55.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101A.

Reference Example 4

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, preparation wasmade in accordance with the same content and manner as in ReferenceExample 3 except that the supply amount of the chloridized andhydrogenated cardanol was changed to 21 g (0.054 mol) to obtain graftedcellulose acetate (19 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.80.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101A.

Reference Example 5

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, preparation wasmade in accordance with the same content and manner as in ReferenceExample 3 except that the supply amount of chloridized and hydrogenatedcardanol was changed to 12 g (0.031 mol) to obtain grafted celluloseacetate (14 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.44.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101A.

Reference Example 6

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, preparation wasmade in accordance with the same content and manner as in ReferenceExample 3 except that the supply amount of the chloridized andhydrogenated cardanol was changed to 6.9 g (0.018 mol) to obtain graftedcellulose acetate (13 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.30.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101A.

Reference Example 7

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetate (tradename: LM-80, manufactured by Daicel Chemical Industries, Ltd., thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, the grafted cellulose acetate wasprepared in accordance with the following procedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (4.1 g (0.011 mol)) prepared in ReferenceSynthesis Example 2 and benzoyl chloride (BC)(2.8 g (0.020 mol))manufactured by Tokyo Kasei Kogyo Co., Ltd. was added. The reactionsolution was heated to reflux at 100° C. for 5 hours. The reactionsolution was slowly added dropwise to methanol (3 L) while stirring toallow reprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate (13 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.30 and DS_(Bc) was 0.14.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 8

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetate (tradename: LM-80, manufactured by Daicel Chemical Industries, Ltd., thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, preparation was made in accordancewith the same content and manner as in Reference Example 7 except thatthe supply amount of the chloridized and hydrogenated cardanol waschanged to 3.1 g (0.008 mol) and the supply amount of benzoyl chloridewas changed to 8.4 g (0.060 mol) to obtain grafted cellulose acetate (14g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.22 and DS_(BC) was 0.27.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 9

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetate (tradename: LM-80, manufactured by Daicel Chemical Industries, Ltd., thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, preparation was made in accordancewith the same content and manner as in Reference Example 7 except thatthe supply amount of the chloridized and hydrogenated cardanol waschanged to 7.6 g (0.020 mol) and the supply amount of benzoyl chloridewas changed to 8.4 g (0.060 mol) to obtain grafted cellulose acetate (16g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.44 and DS_(BC) was 0.22.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 10

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetate (tradename: LM-80, manufactured by Daicel Chemical Industries, Ltd., thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, preparation was made in accordancewith the same content and manner as in Reference Example 7 except thatthe supply amount of the chloridized and hydrogenated cardanol waschanged to 4.1 g (0.011 mol) and the supply amount of benzoyl chloridewas changed to 28.1 g (0.20 mol) to obtain grafted cellulose acetate (15g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.24 and DS_(BC) was 0.42.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 11

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetate (tradename: LM-80, manufactured by Daicel Chemical Industries, Ltd., thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, preparation was made in accordancewith the same content and manner as in Reference Example 7 except thatthe supply amount of the chloridized and hydrogenated cardanol waschanged to 4.6 g (0.012 mol) and the supply amount of benzoyl chloridewas changed to 1.1 g (0.008 mol) to obtain grafted cellulose acetate (14g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.30 and DS_(BC) was 0.07.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 12

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetate (tradename: LM-80, manufactured by Daicel Chemical Industries, Ltd., thenumber of acetic acid molecules added to a single glucose unit ofcellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, preparation was made in accordancewith the same content and manner as in Reference Example 7 except thatthe supply amount of the chloridized and hydrogenated cardanol waschanged to 1.5 g (0.004 mol) and the supply amount of benzoyl chloridewas changed to 2.2 g (0.016 mol) to obtain grafted cellulose acetate (12g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.08 and DS_(BC) was 0.16.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 13

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and biphenylacetyl chloride(BAA) prepared in Reference Synthesis Example 3 as a reactivehydrocarbon were allowed to bind to cellulose acetate (trade name LM-80,manufactured by Daicel Chemical Industries, Ltd., the number of aceticacid molecules added to a single glucose unit of cellulose (degree ofacetylation: DS_(Ace))=2.1) to obtain grafted cellulose acetate. Morespecifically, the grafted cellulose acetate was prepared in accordancewith the following procedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (7.0 g (0.018 mol)) prepared in ReferenceSynthesis Example 2 and biphenylacetyl chloride (BAA) (1.5 g (0.0065mol)) prepared in Reference Synthesis Example 3 was added. The reactionsolution was heated to reflux at 100° C. for 5 hours. The reactionsolution was slowly added dropwise to methanol (3 L) while stirring toallow reprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate (13 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.27 and DS_(BAA) was 0.15.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 14

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and biphenylacetyl chloride(BAA) prepared in Reference Synthesis Example 3 as a reactivehydrocarbon were allowed to bind to cellulose acetate (trade name LM-80,manufactured by Daicel Chemical Industries, Ltd., the number of aceticacid molecules added to a single glucose unit of cellulose (degree ofacetylation: DS_(Ace))=2.1) to obtain grafted cellulose acetate. Morespecifically, preparation was made in accordance with the same contentand manner as in Reference Example 13 except that the supply amount ofthe chloridized and hydrogenated cardanol was changed to 12.2 g (0.032mol) and the supply amount of biphenylacetyl chloride was changed to 4.6g (0.020 mol) to obtain grafted cellulose acetate (14 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.40 and DS_(BAA) was 0.40.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 15

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and biphenylacetyl chloride(BAA) prepared in Reference Synthesis Example 3 as a reactivehydrocarbon were allowed to bind to cellulose acetate (trade name LM-80,manufactured by Daicel Chemical Industries, Ltd., the number of aceticacid molecules added to a single glucose unit of cellulose (degree ofacetylation: DS_(Ace))=2.1) to obtain grafted cellulose acetate. Morespecifically, preparation was made in accordance with the same contentand manner as in Reference Example 13 except that the supply amount ofthe chloridized and hydrogenated cardanol was changed to 15.2 g (0.040mol) and the supply amount of biphenylacetyl chloride was changed to 3.2g (0.014 mol) to obtain grafted cellulose acetate (14 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.55 and DS_(BAA) was 0.28.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 16

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and biphenylacetyl chloride(BAA) prepared in Reference Synthesis Example 3 as a reactivehydrocarbon were allowed to bind to cellulose acetate (trade name:LM-80, manufactured by Daicel Chemical Industries, Ltd., the number ofacetic acid molecules added to a single glucose unit of cellulose(degree of acetylation: DS_(Ace))=2.1) to obtain grafted celluloseacetate. More specifically, preparation was made in accordance with thesame content and manner as in Reference Example 13 except that thesupply amount of the chloridized and hydrogenated cardanol was changedto 7.6 g (0.020 mol) and the supply amount of biphenylacetyl chloridewas changed to 7.4 g (0.032 mol) to obtain grafted cellulose acetate (14g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.30 and DS_(BAA) was 0.52.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101B.

Reference Example 17

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and phenylpropionyl chloride(PPA) as a reactive hydrocarbon were allowed to bind to celluloseacetate (trade name: LM-80, manufactured by Daicel Chemical Industries,Ltd., the number of acetic acid molecules added to a single glucose unitof cellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, the grafted cellulose acetate wasprepared in accordance with the following procedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (4.0 g (0.011 mol)) prepared in ReferenceSynthesis Example 2 and phenylpropionyl chloride (PPA) (2.0 g (0.012mol)) manufactured by Tokyo Kasei Kogyo Co., Ltd. was added. Thereaction solution was heated to reflux at 100° C. for 5 hours. Thereaction solution was slowly added dropwise to methanol (3 L) whilestirring to allow reprecipitation. The resultant solid substance wasseparated by filtration, dried overnight in the air and further driedunder vacuum at 105° C. for 5 hours to obtain grafted cellulose acetate(13 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.17 and DS_(PPA) was 0.25.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Reference Example 18

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and phenylpropionyl chloride(PPA) as a reactive hydrocarbon were allowed to bind to celluloseacetate (trade name: LM-80, manufactured by Daicel Chemical Industries,Ltd., the number of acetic acid molecules added to a single glucose unitof cellulose (degree of acetylation: DS_(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, preparation was made in accordancewith the same content and manner as in Reference Example 17 except thatthe supply amount of the chloridized and hydrogenated cardanol waschanged to 3.8 g (0.010 mol) and the supply amount of phenylpropionylchloride was changed to 2.7 g (0.016 mol) to obtain grafted celluloseacetate (14 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.13 and DS_(PPA) was 0.35.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Reference Example 19

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and cyclohexanecarboxylic acidchloride (CHC) as a reactive hydrocarbon were allowed to bind tocellulose acetate (trade name: LM-80, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.1) toobtain grafted cellulose acetate. More specifically, the graftedcellulose acetate was prepared in accordance with the followingprocedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (3.7 g (0.0096 mol)) prepared in ReferenceSynthesis Example 2 and cyclohexanecarboxylic acid chloride (CHC) (2.5 g(0.017 mol)) manufactured by Sigma-Aldrich Co. LLC was added. Thereaction solution was heated to reflux at 100° C. for 5 hours. Thereaction solution was slowly added dropwise to methanol (3 L) whilestirring to allow reprecipitation. The resultant solid substance wasseparated by filtration, dried overnight in the air and further driedunder vacuum at 105° C. for 5 hours to obtain grafted cellulose acetate(13 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.20 and DS_(CHC) was 0.22.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Reference Example 20

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and biphenylcarbonyl chloride(BCC) as a reactive hydrocarbon were allowed to bind to celluloseacetate (trade name: LM-80, manufactured by Daicel Chemical Industries,Ltd., the number of acetic acid molecules added to a single glucose unitof cellulose (degree of acetylation: DS^(Ace))=2.1) to obtain graftedcellulose acetate. More specifically, the grafted cellulose acetate wasprepared in accordance with the following procedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving the chloridized andhydrogenated cardanol (4.6 g (0.012 mol)) prepared in ReferenceSynthesis Example 2 and biphenylcarbonyl chloride (BCC) (13.0 g (0.060mol)) manufactured by Sigma-Aldrich Co. LLC was added. The reactionsolution was heated to reflux at 100° C. for 5 hours. The reactionsolution was slowly added dropwise to methanol (3 L) while stirring toallow reprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate (16 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.30 and DS_(BCC) was 0.30.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Reference Example 21

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate (trade name: LM-40, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.4) toobtain grafted cellulose acetate. More specifically, the graftedcellulose acetate was prepared in accordance with the followingprocedure.

Cellulose acetate (15.8 g (hydroxy-group amount: 0.036 mol)) wasdissolved in dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml(0.036 mol)) was added as a reaction catalyst and an acid trappingagent. To the solution, a dioxane solution (100 mL) dissolving thechloridized and hydrogenated cardanol (6.8 g (0.018 mol)) prepared inReference Synthesis Example 2 was added. The reaction solution washeated to reflux at 100° C. for 5 hours. The reaction solution wasslowly added dropwise to methanol (3 L) while stirring to allowreprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate (19 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.19.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 102.

Reference Example 22

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate (trade name: L-40, manufactured by Daicel ChemicalIndustries, Ltd., the number of acetic acid molecules added to a singleglucose unit of cellulose (degree of acetylation: DS_(Ace))=2.4) toobtain grafted cellulose acetate. More specifically, grafted celluloseacetate (25 g) was prepared in accordance with the same content andmanner as in Reference Example 21 except that the supply amount ofchloridized and hydrogenated cardanol was changed to 41.2 g (0.108 mol).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.50.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 102.

Reference Example 23

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate butyrate (trade name: CAB-381-20, manufactured byEastman Chemical Company, the number of acetic acid molecules added to asingle glucose unit of cellulose (degree of acetylation: DS_(Ace))=1.0;the number of butyric acid molecules added to a single glucose unit ofcellulose (degree of butyration: DS_(Bu))=1.66) to obtain graftedcellulose acetate butyrate. More specifically, the grafted celluloseacetate butyrate was prepared in accordance with the followingprocedure.

Cellulose acetate butyrate (10 g (hydroxy-group amount: 0.011 mol)) wasdissolved in dehydrated dioxane (200 mL). To this, triethylamine (2.5 ml(0.018 mol)) was added as a reaction catalyst and an acid trappingagent. To the solution, a dioxane solution (100 mL) dissolving thechloridized and hydrogenated cardanol (13 g (0.035 mol)) prepared inReference Synthesis Example 2 was added. The reaction solution washeated to reflux at 100° C. for 5 hours. The reaction solution wasslowly added dropwise to methanol (3 L) while stirring to allowreprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate butyrate (13 g).

The obtained sample (grafted cellulose acetate butyrate) was measured by¹H-NMR (product name: AV-400, 400 MHz, manufactured by Bruker), andDS_(CD) was 0.34.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 103.

Reference Example 24

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 was allowed to bind tocellulose acetate propionate (trade name: CAP-482-20, manufactured byEastman Chemical Company, the number of acetic acid molecules added to asingle glucose unit of cellulose (degree of acetylation: DS_(Ace))=0.18;the number of propionic acid molecules added to a single glucose unit ofcellulose (degree of propionation: DS_(Pr))=2.49) to obtain graftedcellulose acetate propionate. More specifically, the grafted celluloseacetate propionate was prepared in accordance with the followingprocedure.

Cellulose acetate propionate (10 g (hydroxy-group amount: 0.010 mol))was dissolved in dehydrated dioxane (200 mL). To this, triethylamine(2.5 ml (0.018 mol)) was added as a reaction catalyst and an acidtrapping agent. To the solution, a dioxane solution (100 mL) dissolvingthe chloridized and hydrogenated cardanol (13 g (0.035 mol)) prepared inReference Synthesis Example 2 was added. The reaction solution washeated to reflux at 100° C. for 5 hours. The reaction solution wasslowly added dropwise to methanol (3 L) while stirring to allowreprecipitation. The resultant solid substance was separated byfiltration, dried overnight in the air and further dried under vacuum at105° C. for 5 hours to obtain grafted cellulose acetate propionate (13g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(CD) was0.33.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 103.

Reference Example 25

The chloridized and hydrogenated cardanol (cardanol derivative 2)prepared in Reference Synthesis Example 2 and benzoyl chloride (BC) as areactive hydrocarbon were allowed to bind to cellulose acetatepropionate (trade name: CAP-482-20, manufactured by Eastman ChemicalCompany, the number of acetic acid molecules added to a single glucoseunit of cellulose (degree of acetylation: DS_(Ace))=0.18; the number ofpropionic acid molecules added to a single glucose unit of cellulose(degree of propionation: DS_(Pr))=2.49) to obtain grafted celluloseacetate propionate. More specifically, the grafted cellulose acetatepropionate was prepared in accordance with the following procedure.

Cellulose acetate propionate (10 g (hydroxy-group amount: 0.010 mol))was dissolved in dehydrated dioxane (200 mL). To this, triethylamine(2.5 ml (0.018 mol)) was added as a reaction catalyst and an acidtrapping agent. To the solution, a dioxane solution (100 mL) dissolvingthe chloridized and hydrogenated cardanol (4.5 g (0.012 mol)) preparedin Reference Synthesis Example 2 and benzoyl chloride (BC) (2.8 g (0.020mol)) manufactured by Tokyo Kasei Kogyo Co., Ltd. was added. Thereaction solution was heated to reflux at 100° C. for 5 hours. Thereaction solution was slowly added dropwise to methanol (3 L) whilestirring to allow reprecipitation. The resultant solid substance wasseparated by filtration, dried overnight in the air and further driedunder vacuum at 105° C. for 5 hours to obtain grafted cellulose acetatepropionate (13 g).

The obtained sample (grafted cellulose acetate propionate) was measuredby ¹H-NMR (product name: AV-400, 400 MHz, manufactured by Bruker), andDS_(CD) was 0.21 and DS_(BC) was 0.10.

Furthermore, the sample was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 103.

Reference Example 26

Hydrogenated cardanol (m-n-pentadecylphenol manufactured by ACROSOrganics), in which an unsaturated bond(s) of the straight-chainhydrocarbon moiety of cardanol are hydrogenated, was used as a rawmaterial. The phenolic hydroxy group of the cardanol was reacted withmonochloroacetic acid to add a carboxyl group to obtain carboxylated andhydrogenated cardanol. More specifically, the carboxylated andhydrogenated cardanol was prepared in accordance with the followingprocedure.

First, hydrogenated cardanol (80 g (0.26 mol)) was dissolved in methanol(120 mL). To this, an aqueous solution dissolving sodium hydroxide (64 g(1.6 mol)) in distilled water (40 mL) was added. Thereafter, at roomtemperature, a solution of monochloro acetic acid (66 g (0.70 mol))manufactured by Kanto Chemical Co., Inc. dissolved in methanol (50 mL)was added dropwise. After completion of the dropwise addition, thereaction solution was continuously stirred while refluxing at 73° C. for4 hours. The reaction solution was cooled to room temperature and thereaction mixture was acidified with a diluted hydrochloric acid until pHbecame 1. To this, methanol (250 mL) and diethyl ether (500 mL) andfurther distilled water (200 mL) were added. The resultant water layerwas separated by a separating funnel and discarded. The ether layer waswashed twice with distilled water (400 mL). To the ether layer,magnesium anhydride was added to dry the ether layer and then separatedby filtration. The filtrate (ether layer) was concentrated by anevaporator (90° C./3 mmHg) under reduced pressure to obtain a yellowbrown powdery crude product as the residue. The crude product wasrecrystallized from n-hexane and dried under vacuum to obtain whitepowder of carboxylated and hydrogenated cardanol (46 g (0.12 mol)).

The carboxylated and hydrogenated cardanol thus prepared was allowed tobind to cellulose (trade name: KC Flock W-50G manufactured by NipponPaper Chemicals) to obtain grafted cellulose. More specifically, thegrafted cellulose was prepared in accordance with the followingprocedure.

Cellulose (2.5 g (hydroxy-group amount: 47 mmol)) was suspended inmethanol (100 mL) and stirred for one hour at room temperature andfiltrated by suction. The solid substance separated by filtration wasallowed to swell with dimethylacetamide (DMAc) (100 mL), stirred onehour at room temperature and filtrated by suction to remove the solvent.Thereafter, swelling with DMAc and solvent removal by suction filtrationwere repeated three times in the same manner. LiCl (21 g) was dissolvedin DMAc (250 mL) and the DMAc-swollen cellulose previously obtained wasmixed and stirred at room temperature overnight to obtain a cellulosesolution. To the cellulose solution thus obtained, a DMAc solution (20mL) dissolving the carboxylated and hydrogenated cardanol (17.3 g (46.5mmol)), pyridine (11.0 g (140 mmol)) and tosyl chloride (8.8 g (46mmol)) was added. The reaction solution was reacted by heating at 50° C.for one hour. The reaction solution was added dropwise to methanol (2 L)to allow reprecipitation. The resultant solid substance was separated byfiltration, washed three times with methanol (500 mL) and dried undervacuum at 105° C. for 5 hours to obtain grafted cellulose (10.4 g).DS_(CD) was obtained from the yield, and DS_(CD) was 1.49. Furthermore,the sample was evaluated in the same manner as in Reference Example 1.The results are shown in Table 104.

Reference Comparative Example 1

The same cellulose acetate before grafting as that used in ReferenceExample 1 was used as a comparative sample.

The cellulose acetate was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Note that the cellulose acetate did not melt even if heated and did notexhibit thermoplasticity. Furthermore, since the cellulose acetate couldnot be molded, a bending test was not performed.

Reference Comparative Example 2

To the same cellulose acetate before grafting as that used in ReferenceExample 1, triethyl citrate (trade name: Citroflex-2 manufactured byPfizer Inc.) was added as a plasticizer such that the content became 45%by mass based on the whole resin composition. This was mixed by anextruder mixer (HAAKE MiniLab Rheomex extruder (Model CTW5, ThermoElectron Corp., Waltham, Mass.)) at a temperature of 200° C. and a screwrotation speed of 60 rpm to prepare a cellulose acetate resincomposition.

The resin composition was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Note that when the resin composition was casted, a phase separationoccurred and a uniform film could not be prepared. Thus, a tensile testwas not performed.

Reference Comparative Example 3

A cellulose acetate resin composition was prepared in accordance withthe same content and manner as in Reference Comparative Example 2 exceptthat the addition amount of triethyl citrate was set to 56% by massbased on the whole resin composition.

The resin composition was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Note that when the resin composition was casted, a phase separationoccurred and a uniform film could not be prepared. Thus, a tensile testwas not performed.

Reference Comparative Example 4

A cellulose acetate resin composition was prepared in accordance withthe same content and manner as in Reference Comparative Example 2 exceptthat the addition amount of triethyl citrate was set to 34% by massbased on the whole resin composition.

The resin composition was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 101C.

Note that when the resin composition was casted, a phase separationoccurred and a uniform film could not be prepared. Thus, a tensile testwas not performed.

Reference Comparative Example 5

Phenylpropionyl chloride (PPA) was used as a reactive hydrocarbon andallowed to bind to cellulose acetate (trade name: LM-80, manufactured byDaicel Chemical Industries, Ltd., the number of acetic acid moleculesadded to a single glucose unit of cellulose (degree of acetylation:DS_(Ace))=2.1) to obtain grafted cellulose acetate. More specifically,the grafted cellulose acetate was prepared in accordance with thefollowing procedure.

Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol)) was dissolvedin dehydrated dioxane (200 mL). To this, triethylamine (5.0 ml (0.036mol)) was added as a reaction catalyst and an acid trapping agent. Tothe solution, a dioxane solution (100 mL) dissolving phenylpropionylchloride (PPA) (10 g (0.060 mol)) manufactured by Tokyo Kasei Kogyo Co.,Ltd., was added. The reaction solution was heated to reflux at 100° C.for one hour. The reaction solution was slowly added dropwise tomethanol (3 L) while stirring to allow reprecipitation. The resultantsolid substance was separated by filtration, dried overnight in the airand further dried under vacuum at 105° C. for 5 hours to obtain graftedcellulose acetate (12 g).

The obtained sample (grafted cellulose acetate) was measured by ¹H-NMR(product name: AV-400, 400 MHz, manufactured by Bruker), and DS_(PPA)was 0.47.

The sample was evaluated in the same manner as in Reference Example 1.The results are shown in Table 101C.

Note that the cellulose acetate did not melt even if heated and did notexhibit thermoplasticity. Furthermore, since the cellulose acetate couldnot be molded, a bending test was not performed.

Reference Comparative Example 6

The same cellulose acetate before grafting (DS_(Ace)=2.4) as that usedin Reference Example 21 was used as a comparative sample.

The cellulose acetate was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 102.

Note that the cellulose acetate did not melt even if heated and did notexhibit thermoplasticity. Furthermore, since the cellulose acetate couldnot be molded, a bending test was not performed.

Reference Comparative Example 7

To the same cellulose acetate (DS_(Ace)=2.4) before grafting as thatused in Reference Example 21, triethyl citrate (trade name: Citroflex-2manufactured by Pfizer Inc.) was added as a plasticizer such that thecontent became 20% by mass based on the whole resin composition. Thiswas mixed by an extruder mixer (HAAKE MiniLab Rheomex extruder (ModelCTW5, Thermo Electron Corp., Waltham, Mass.)) at a temperature of 190°C. and a screw rotation speed of 60 rpm) to prepare a cellulose acetateresin composition.

The resin composition was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 102.

Note that when the resin composition was casted, a phase separationoccurred and a uniform film could not be prepared. Thus, a tensile testwas not performed.

Reference Comparative Example 8

A cellulose acetate resin composition was prepared in accordance withthe same content and manner as in Reference Comparative Example 7 exceptthat the addition amount of triethyl citrate was set to 40% by massbased on the whole resin composition.

The resin composition was evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 102.

Note that when the resin composition was casted, a phase separationoccurred and a uniform film could not be prepared. Thus, a tensile testwas not performed.

Reference Comparative Examples 9 and 10

The same cellulose acetate butyrate and cellulose acetate propionatebefore grafting as those that used in Reference Examples 23 and 24 wereused as comparative samples respectively.

The cellulose acetate butyrate and cellulose acetate propionate wereevaluated in the same manner as in Reference Example 1. The results areshown in Table 103.

Note that the cellulose acetate butyrate and cellulose acetatepropionate melted when heated. They had thermoplasticity; however, meltviscosity was extremely large. Since it was difficult to mold them, abending test was not performed.

Reference Comparative Examples 11 and 12

To each of the same cellulose acetate butyrate and cellulose acetatepropionate before grafting as those used in Reference Examples 23 and 24respectively, triethyl citrate (trade name: Citroflex-2 manufactured byPfizer Inc.) was added as a plasticizer such that the content became 27%by mass based on the whole resin composition. This was mixed by anextruder mixer (HAAKE MiniLab Rheomex extruder (Model CTW5, ThermoElectron Corp., Waltham, Mass.)) at a temperature of 180° C. and a screwrotation speed of 60 rpm to prepare a cellulose acetate butyrate resincomposition and a cellulose acetate propionate resin composition.

The resin compositions were evaluated in the same manner as in ReferenceExample 1. The results are shown in Table 103.

Note that when each of the resin compositions was casted, a phaseseparation occurred and a uniform film could not be prepared. Thus, atensile test was not performed.

Reference Comparative Example 13

To compare with Reference Example 26, a resin composition composed ofcellulose acetate and triethyl citrate as a plasticizer was prepared inaccordance with the same manner as in Reference Comparative Example 2except that the addition amount of the plasticizer was changed to 63% bymass based on the whole resin composition. The total amount ofplasticizer and acetyl group was set to be equal to the amount ofcardanol of Reference Example 26. The resin composition was evaluated inthe same manner as in Reference Example 1. The results are shown inTable 104.

Note that when the resin composition was casted, a phase separationoccurred and a uniform film could not be prepared. Thus, a tensile testwas not performed.

Reference Comparative Example 14

An unsaturated bond of cardanol represented by the above Formula (2)(LB-7000: a mixture of 3-pentadecylphenol (about 5%), 3-pentadecylphenolmonoene (about 35%), 3-pentadecylphenol diene (about 20%),3-pentadecylphenol triene (about 40%); manufactured by Tohoku ChemicalIndustries, Ltd.) was chemically bound to a hydroxy group of a cellulose(trade name: KC Flock W-50G manufactured by Nippon Paper Chemicals) toobtain cardanol-grafted cellulose. More specifically, thecardanol-grafted cellulose was prepared in accordance with the followingprocedure.

In a dry box, a reaction solvent was prepared from borontrifluoridediethyl ether (BF₃—OEt₂) (manufactured by Kanto Chemical Co., Inc.) (80mL) and methylene chloride (100 mL) (manufactured by Kanto Chemical Co.,Inc.) under a nitrogen gas atmosphere. To this, cellulose (2 g) wasadded and the mixture was stirred at room temperature for 2 hours.Thereafter, the cellulose was separated by filtration from the reactionsolvent and dried under vacuum. Thereafter, to this, liquid-statecardanol (LB-7000) (100 mL) as mentioned above was added and a graftingreaction was performed while stirring at room temperature for 3 hours.After completion of the reaction, a product was separated by filtration,washed with acetone, extracted by Soxhlet and dried under vacuum at 105°C. for 5 hours to obtain a desired cardanol-grafted cellulosecomposition (2.5 g). DS_(CD) was obtained from a yield, and DS_(CD) was0.16.

Note that the composition did not melt even if heated and did notexhibit thermoplasticity. Furthermore, since the composition could beneither molded nor casted, evaluation, such as a bending test andtensile test, was not performed.

TABLE 101A Reference Reference Reference Reference Reference ReferenceExample 1 Example 2 Example 3 Example 4 Example 5 Example 6 Amount ofacetyl DS_(Ace) 2.1 2.1 2.1 2.1 2.1 2.1 group Mass fraction (%) 16 20 2121 23 26 Amount of DS_(CD) 0.90 0.55 0 0 0 0 cardanol modified withsuccinic acid derivative DS_(CD) 0 0 0.55 0.80 0.44 0.30 modified withmonochloro acetic acid Mass fraction (%) 56 46 43 53 38 29 Amount ofDS_(XX) 0 0 0 0 0 0 reactive Mass fraction (%) 0 0 0 0 0 0 hydrocarboncompound Addition amount of plasticizer 0 0 0 0 0 0 (% by mass) Bendingstrength (MPa) 38 48 50 36 60 83 Bending elastic modulus (GPa) 0.80 1.11.2 0.80 1.4 1.9 Bend-breaking strain (%) >10 >10 >10 >10 >10 >10Tensile strength (MPa) 29 36 38 27 45 59 Tensile elastic modulus (GPa)0.6 0.9 1.0 0.6 1.2 1.7 Tensile breaking strain (%) 57 55 53 57 51 48Glass transition temperature (° C.) 125 134 147 139 142 150 (heatresistance) Thermoplasticity (press moldability) ◯ ◯ ◯ ◯ ◯ ◯ Waterabsorption rate (%) 1.1 1.5 1.2 0.94 1.3 1.7 Plant component ratio (%)71 70 73 76 72 71

TABLE 101B Reference Reference Reference Reference Reference ReferenceReference Reference Reference Reference Example Example Example ExampleExample Example Example Example 7 Example 8 Example 9 10 11 12 13 14 1516 Amount of DS_(Ace) 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 acetylMass 25 26 21 24 25 31 24 20 18 20 group fraction (%) Amount of DS_(CD)0 0 0 0 0 0 0 0 0 0 cardanol modified derivative with succinic acidDS_(CD) 0.30 0.22 0.44 0.24 0.30 0.08 0.27 0.40 0.55 0.30 modified withmonochloro acetic acid Mass 28 22 36 22 29 9.4 25 30 39 23 fraction (%)Amount of DS_(XX) xx = BC xx = BC xx = BC xx = BC xx = BC xx = BC xx =BAA xx = BAA xx = BAA xx = BAA reactive 0.14 0.27 0.22 0.42 0.07 0.160.15 0.40 0.28 0.52 hydro- Mass fraction (%) 4.0 8.0 5.4 12 1.8 5.7 7.316 11 21 carbon compound Addition amount 0 0 0 0 0 0 0 0 0 0 ofplasticizer (% by mass) Bending strength (MPa) 113 118 106 112 94 95 106107 93 95 Bending elastic 2.2 2.6 2.1 2.2 1.9 2.9 2.5 2.0 1.9 2.1modulus (GPa) Bend-breaking strain (%) >10 >10 >10 >10 >106.5 >10 >10 >10 >10 Tensile strength (MPa) 69 72 66 70 64 75 65 65 63 64Tensile elastic 1.6 1.8 1.6 1.6 1.5 1.9 1.8 1.5 1.4 1.6 modulus (GPa)Tensile breaking 48 47 52 47 50 30 45 46 48 45 strain (%) Glasstransition 154 155 144 156 152 158 148 150 142 147 temperature (° C.)(heat resistance) Thermoplasticity ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ (pressmoldability) Water absorption rate (%) 1.3 1.6 1.1 1.2 1.4 1.9 1.0 0.720.68 0.65 Plant component ratio (%) 68 64 68 61 69 62 65 60 66 55

TABLE 101C Reference Reference Reference Reference Reference ReferenceReference Reference Reference Example Example Example ExampleComparative Comparative Comparative Comparative Comparative 17 18 19 20Example 1 Example 2 Example 3 Example 4 Example 5 Amount of DS_(Ace) 2.12.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 acetyl group Mass fraction 26 27 26 2236 20 16 24 29 (%) Amount of DS_(CD) 0 0 0 0 0 0 0 0 0 cardanol modifiedwith derivative succinic acid DS_(CD) 0.17 0.13 0.20 0.30 0 0 0 0 0modified with monochloro acetic acid Mass fraction 17 13 20 25 0 0 0 0 0(%) Amount of DS_(XX) xx = PPA xx = PPA xx = CHC xx = BCC 0 0 0 0 xx =PPA reactive 0.25 0.35 0.22 0.30 0.47 hydrocarbon Mass fraction 9.7 147.1 13 0 0 0 0 20 compound (%) Addition amount of plasticizer 0 0 0 0 045 56 34 0 (% by mass) Bending strength (MPa) 106 108 111 109 — 15 11 24— Bending elastic modulus 2.5 2.6 2.5 2.5 — 0.41 0.29 0.72 — (GPa)Bend-breaking strain (%) >10 >10 >10 >10 — >10 >10 >10 — Tensilestrength (MPa) 65 66 68 67 60 — — — 52 Tensile elastic modulus (GPa) 1.41.4 1.6 1.5 2.3 — — — 1.9 Tensile breaking strain (%) 60 58 55 50 9.0 —— — 16 Glass transition temperature 143 142 146 150 227 40 25 71 152 (°C.) (heat resistance) Thermoplasticity ◯ ◯ ◯ ◯ X ◯ ◯ ◯ X (pressmoldability) Water absorption rate (%) 1.9 1.8 1.8 1.4 17 5.1 4.3 5.74.5 Plant component ratio (%) 61 58 64 65 64 35 28 42 51

TABLE 102 Reference Reference Reference Reference Reference ComparativeComparative Comparative Example 21 Example 22 Example 6 Example 7Example 8 Amount of DS_(Ace) 2.4 2.4 2.4 2.4 2.4 acetyl group Massfraction (%) 31 24 31 39 24 Amount of DS_(CD) 0.19 0.50 0 0 0 cardanolmodified with derivative monochloro acetic acid Mass fraction (%) 20 400 0 0 Addition amount of plasticizer 0 0 0 20 40 (% by mass) Bendingstrength (MPa) 120 59 — 50 20 Bending elastic modulus (GPa) 2.8 1.5 —2.3 0.80 Bend-breaking strain (%) >10 >10 — >10 >10 Tensile strength(MPa) 55 38 58 — — Tensile elastic modulus (GPa) 1.8 1.0 2.1 — — Tensilebreaking strain (%) 34 53 11 — — Glass transition temperature (° C.) 154134 216 90 63 (heat resistance) Thermoplasticity (press moldability) ◯ ◯X ◯ ◯ Water absorption rate (%) 2.1 1.2 9.0 3.1 2.6 Plant componentratio (%) 66 71 61 49 36

TABLE 103 Reference Reference Reference Reference Reference ReferenceReference Example Example Example Comparative Comparative ComparativeComparative 23 24 25 Example 9 Example 10 Example 11 Example 12 Amountof acetyl DS_(Ace) 1.0 0.18 0.18 1.0 0.18 1.0 0.18 group Mass fraction(%) 9.8 1.8 2.0 13 2.5 9.8 1.8 Amount of DS_(Bu) or DS_(Pr) DS_(Bu)DS_(Pr) DS_(Pr) DS_(Bu) DS_(Pr) DS_(Bu) DS_(Pr) butyryl/ 1.66 2.49 2.491.66 2.49 1.66 2.49 propionyl group Mass fraction (%) 27 27 36 37 46 2734 Amount of DS_(CD) 0.34 0.33 0.21 0 0 0 0 cardanol modified withderivative monochloro acetic acid Mass fraction (%) 27 27 19 0 0 0 0Amount of DS_(XX) 0 0 xx = BC 0 0 0 0 reactive 0.10 hydrocarbon Massfraction (%) 0 0 2.7 0 0 0 0 compound Addition amount of plasticizer 0 00 0 0 27 27 (% by mass) Bending strength (MPa) 45 49 60 — — 23 15Bending elastic modulus (GPa) 1.3 1.4 1.6 — — 0.79 0.82 Bend-breakingstrain (%) >10 >10 >10 — — >10 >10 Tensile strength (MPa) 35 39 43 36 40— — Tensile elastic modulus (GPa) 0.85 0.87 1.0 1.0 1.1 — — Tensilebreaking strain (%) 100 98 82 55 52 — — Glass transition temperature (°C.) 94 92 100 135 143 59 59 (heat resistance) Thermoplasticity (pressmoldability) ◯ ◯ ◯ Δ Δ ◯ ◯ Water absorption rate (%) 0.65 0.76 0.74 2.63.1 1.5 1.6 Plant component ratio (%) 60 61 57 50 52 36 38

TABLE 104 Reference Reference Comparative Example 26 Example 13 Amountof cellulose Mass fraction (%) 24 24 Amount of acetyl DS_(Ace) 0 2.1group Mass fraction (%) 0 13 Amount of cardanol DS_(CD) 1.49 0derivative modified with monochloro acetic acid Mass fraction (%) 76 0Addition amount of plasticizer 0 63 (% by mass) Bending strength (MPa)25 9 Bending elastic modulus (GPa) 0.38 0.20 Bend-breaking strain(%) >10 >10 Tensile strength (MPa) 17 — Tensile elastic modulus (GPa)0.26 — Tensile breaking strain (%) 22 — Glass transition temperature (°C.) 84 21 (heat resistance) Thermoplasticity (press moldability) ◯ ◯Water absorption rate (%) 1.9 4.0 Plant component ratio (%) 89 24

When Reference Examples 1 to 6 are compared to Reference ComparativeExample 1, the cardanol-grafted cellulose resins (an acetyl group isalso added to a cellulose hydroxy group) of the reference examples eachhad thermoplasticity (press moldability) and excellent bendingproperties without reducing a plant component ratio, and further tensileproperties (particularly, breaking strain) and water resistance (waterabsorption rate) were improved, compared to the cellulose derivative(cellulose acetate) before grafting which had no thermoplasticity.Furthermore, when Reference Examples 1 to 6 are compared to ReferenceComparative Examples 2 to 4, the cardanol-grafted cellulose resins (anacetyl group is also added to a cellulose hydroxy group) of thereference examples were more improved in bending properties, tensileproperties and water resistance than the cellulose derivatives beforegrafting (cellulose acetate) which contained the plasticizer. Inaddition, high heat resistance (glass transition temperature) wasobtained without reducing the plant component ratio.

As shown in Reference Examples 7 to 20, bending properties(particularly, bending strength) and tensile properties (particularly,tensile strength) can be even more improved while obtaining high waterresistance by grafting with not only cardanol but also a reactivehydrocarbon.

In Reference Examples 21 and 22 and Reference Comparative Examples 6 to8, compared to Reference Examples 1 to 20 and Reference ComparativeExamples 1 to 5, the amount of acetyl group added to a hydroxy group ofcellulose is increased. Even in these case, when Reference Examples 21and 22 are compared to Reference Comparative Example 6, thecardanol-grafted cellulose resins of the reference examples each hadthermoplasticity and excellent bending properties without reducing aplant component ratio, and further tensile properties (particularly,breaking strain) and water resistance were improved, compared to thecellulose derivative before grafting which had no thermoplasticity.Furthermore, when Reference Examples 21 and 22 are compared to ReferenceComparative Examples 7 and 8, the cardanol-grafted cellulose resins ofthe reference examples were more improved in bending properties(particularly, bending strength), tensile properties and waterresistance than the cellulose derivatives before grafting whichcontained the plasticizer. In addition, high heat resistance wasobtained without reducing the plant component ratio.

As shown in Reference Comparative Examples 2 to 4, 7 and 8 containingplasticizer, excellent heat resistance was not obtained by adding theplasticizer alone. According to the reference examples, not onlythermoplasticity can be imparted to a cellulose resin but also excellentheat resistance can be obtained.

Furthermore, as shown in Reference Comparative Example 5 in which areactive hydrocarbon alone was grafted, thermoplasticity was notobtained only by grafting a reactive hydrocarbon alone, and bendingproperties, tensile properties (particularly, breaking strain) and waterresistance were not improved. According to the reference example, notonly thermoplasticity can be imparted to a cellulose resin but alsoexcellent bending properties, tensile properties (particularly, breakingstrain) and water resistance can be obtained.

Reference Examples 23 to 25 and Reference Comparative Examples 9 to 12,each are an example of a cellulose resin prepared by using a cellulosederivative having not only an acetyl group but also a butyryl group or apropionyl group added to a hydroxy group. Even in these case, whenReference Examples 23 to 25 are compared to Reference ComparativeExamples 9 and 10, in the cardanol-grafted cellulose resins of thereference examples, excellent thermoplasticity and bending propertieswere obtained without reducing the plant component ratio, and furthertensile properties (particularly breaking strain) and water resistancewere improved, compared to the cellulose derivatives before grafting.Furthermore, when Reference Examples 23 to 25 and Reference ComparativeExamples 11 and 12 are compared, the cardanol-grafted cellulose resinsof the reference examples were more improved in bending properties(particularly, bending strength), tensile properties and waterresistance than the cellulose derivatives before grafting whichcontained the plasticizer. In addition, high heat resistance wasobtained without reducing the plant component ratio.

Reference Example 26 is an example of a cellulose resin prepared byusing cellulose having a hydroxy group of cellulose to which an acylgroup such as an acetyl group is not added. Even in this case, whenReference Example 26 is compared to Reference Comparative Example 13,the cardanol-grafted cellulose resin of the reference example was moreimproved in bending properties (particularly, bending strength), tensileproperties and water resistance than the cellulose derivative ofReference Comparative Example 13, in which the cellulose derivative(cellulose acetate) contained a plasticizer (the weight ratio of thecellulose component is the same as the Reference Example 26). Inaddition, high heat resistance was obtained without reducing the plantcomponent ratio.

As described above, according to the reference examples, it is possibleto provide a cellulose resin improved in water resistance and havinggood thermoplasticity (press moldability) and sufficient heat resistancewhile maintaining a high plant component ratio (high vegetism).Furthermore, a press molded product having high bending properties canbe obtained and a film molded product can be improved in tensileproperties (particularly, toughness). Furthermore, according to thereference examples, a grafted cellulose resin having a high plantcomponent ratio as well as high utilization ratio of non-edible partscan be obtained.

While the present invention has been described with reference to theexemplary embodiments and examples, the present invention is not limitedto the above exemplary embodiments and examples. Various changes thatcan be understood by those skilled in the art may be made to theconstitution and details of the present invention within the scopethereof.

This application claims the right of priority based on Japanese PatentApplication No. 2011-082969 filed on Apr. 4, 2011 and Japanese PatentApplication No. 2011-198743 filed on Sep. 12, 2011, the entire contentof which are incorporated herein by reference.

1. A cellulose resin produced by binding a hydrogenated cardanolcomprising 3-pentadecylcyclohexanol, and cellulose or a derivativethereof through a reaction between a hydroxy group of the hydrogenatedcardanol, a hydroxy group of the cellulose or a derivative thereof andisocyanate groups of a diisocyanate compound.
 2. The cellulose resinaccording to claim 1, wherein the diisocyanate compound is a compoundcomprising a hydrocarbon group having 3 to 20 carbon atoms to which twoisocyanate groups are bound.
 3. The cellulose resin according to claim1, wherein the diisocyanate compound is an aliphatic diisocyanatecomprising a straight-chain alkylene chain having 3 to 12 carbon atomsto both end carbon atoms of which an isocyanate group is bound.
 4. Thecellulose resin according to claim 1, wherein the number of thehydrogenated cardanol added to the cellulose or a derivative thereof perglucose unit thereof, DS_(CD), is 0.1 or more.
 5. The cellulose resinaccording to claim 1, wherein the number of remaining hydroxy groups perglucose unit of the cellulose or a derivative thereof, DS_(OH), is 0.9or less.
 6. A resin composition containing the cellulose resin accordingto claim 1 as a base resin.
 7. A molding material comprising the resincomposition according to claim
 6. 8. A method for producing a celluloseresin, comprising: binding a hydrogenated cardanol comprising3-pentadecylcyclohexanol, and a diisocyanate compound by reacting ahydroxy group of the hydrogenated cardanol and an isocyanate group ofthe diisocyanate compound to form a diisocyanate-added cardanolderivative, and binding the diisocyanate-added cardanol derivative andcellulose or a derivative thereof by reacting an isocyanate group of thediisocyanate-added cardanol derivative and a hydroxy group of thecellulose or a derivative thereof.
 9. The method for producing acellulose resin according to claim 8, wherein the diisocyanate compoundis a compound comprising a hydrocarbon group having 3 to 20 carbon atomsto which two isocyanate groups are bound.
 10. The method for producing acellulose resin according to claim 8, wherein, in the step of bindingthe diisocyanate-added cardanol derivative and the cellulose or aderivative thereof, a solvent having a polarity value (RelativePolarity) of 0.15 or more and 0.5 or less is used.
 11. The celluloseresin according to claim 2, wherein the number of the hydrogenatedcardanol added to the cellulose or a derivative thereof per glucose unitthereof, DS_(CD), is 0.1 or more.
 12. The cellulose resin according toclaim 3, wherein the number of the hydrogenated cardanol added to thecellulose or a derivative thereof per glucose unit thereof, DS_(CD), is0.1 or more.
 13. The cellulose resin according to claim 2, wherein thenumber of remaining hydroxy groups per glucose unit of the cellulose ora derivative thereof, DS_(OH), is 0.9 or less.
 14. The cellulose resinaccording to claim 3, wherein the number of remaining hydroxy groups perglucose unit of the cellulose or a derivative thereof, DS_(OH), is 0.9or less.
 15. The cellulose resin according to claim 4, wherein thenumber of remaining hydroxy groups per glucose unit of the cellulose ora derivative thereof, DS_(OH), is 0.9 or less.
 16. A resin compositioncontaining the cellulose resin according to claim 2 as a base resin. 17.A resin composition containing the cellulose resin according to claim 3as a base resin.
 18. A resin composition containing the cellulose resinaccording to claim 4 as a base resin.
 19. A resin composition containingthe cellulose resin according to claim 5 as a base resin.